Composites for resist removal and methods of electric devices manufacturing

FIELD: electricity.

SUBSTANCE: invention is related to manufacturing method of electric devices that includes the following stages: 1) application of insulating dielectric layer consisting of one material with low and ultralow dielectric permeability to substrate surface; 2) application of positive or negative resist coating to surface of insulating dielectric layer; 3) subject of resist coating to selective impact of electromagnetic radiation or corpuscular radiation; 4) development of selective radiated resist coating in order to form a pattern in resist; 5) dry etching of insulating dielectric layer using pattern in resist as mask for formation of wire channels and/or feedthrough openings communicated with substrate surface; 6) selection of at least one polar organic solution (A) from the group consisting of diethylenetriamine, N-methyl imidazole, 3-amine-1-propanol, 5-amine-1-pentanol and dimethyl sulfoxide developing in presence of 0.06 up to 4 wt % of dissolved hydroxide tetramethylammonium (B), which mass fraction is taken on the basis of full weight of the respective tested solution, permanent intensity of removal at 50°C for polymer barrier antireflecting coating with thickness of 30nm that contains chromophoric groups absorbing deep UV light; 7) provision of at least one composite for resist removal that does not contain N-alkyl pyrrolidone and hydroxylamine and hydroxylamine derivants and has dynamic shear viscosity at 50°C from 1 up to 10mPa·s measured by rotating-cylinder technique, and contains, based on the full weight of the composite, (A) from 40 up to 99.95 wt % of at least one polar organic solution selected in compliance with the process stage (6), (B) from 0.05 up to <0.5 wt % of at least one quaternary ammonium hydroxide, based on full weight of the composite, and (C) < 5 wt % of water, based on full weight of the composite; 8) removal of resist pattern and smutty residue by means of damp process using at least one composite for resist removal (7) produced in compliance with the process stage (7); and 9) filling of wire channels (5) and feedthrough openings (5) with at least one material having low electric resistance. The invention is also related to usage of this composite.

EFFECT: composite is capable of removal of positive and negative photo resists and PER in identical and the most advantageous way without damage of surface layers of wafers, relief structures of wafers and gluing material connecting thin silicon wafers with substrates.

14 cl, 3 tbl, 4 ex

 

Field of the invention

The present invention relates to new compositions for the removal of the resist useful for the removal of structured resists from substrates, in particular semiconductor substrates containing copper and materials with low (low-k) or ultra-low (ultra low-k) dielectric constants.

Moreover, the present invention concerns new methods of manufacturing electrical devices, particularly semiconductor integrated circuits (IC), liquid crystal display panels, organic electroluminescent display panels, printed circuit boards, micro machines, DNA chips and micro plants, mainly IP, new ways of obtaining using a new composition for the removal of the resist.

The level of technology

Resists, such as photoresists sensitive to far ultraviolet radiation, or electron resists are used in microlithographic the method of manufacturing a wide range of electrical devices such as semiconductor integrated circuits (IC), liquid crystal display panels, organic electroluminescent display panels, printed circuit boards, micro machines, DNA chips and micro plants, mostly IP with LSI (high degree of integration) or VLSI (very high degree of integration).

Currently copper is traditionally used in quality�e material with low electrical resistance or as a material for wiring in electrical devices in particular in the cross-connections and interconnections contained in IP. The growing use of copper and decreasing the size of electrical structures, coupled with ever-increasing functionality of IP require the use of materials with low and ultra-low dielectric constant in order to avoid problems with resistance wiring and a delay in the wired connection, due to the large capacities of the installation. These promising developments have required and still require constant optimization of manufacturing methods and the involved materials.

When forming a copper metal wiring, in particular, applies a process in which copper multilayer wiring is formed without etching of copper by applying a dual process demaskirovanie (dual-damascene process). Due to the low resistance to etching of copper have been proposed various kinds of dual processes demaskirovanie. One such example includes the formation of a copper layer and forming a layer with a low dielectric constant (e.g., storage I / o control layer) on top of the copper layer followed by the formation of the resist layer as the top layer. Not necessarily before application of the resist layer on the surface layer with a low dielectric constant can b�th formed layer of metal nitride (e.g., TiN layer). In another embodiment, the barrier anti-reflective layer (BARC) is placed between the layer of nitride of the metal and the resist layer.

Subsequently, the resist layer is selectively exposed to electromagnetic radiation or to electron flow and is processed to form the image in the resist layer (first pattern in the photoresist layer").

Then, using the first pattern in the photoresist layer as a pattern mask, the layer with low and ultra-low dielectric partially dry etched by applying a fluorine-containing plasma. The simultaneous use of a layer of a nitride of the metal at this stage of the process is traditionally referred to as "method of the hard mask. Then the first pattern in the photoresist layer is removed by ashing in oxygen plasma. Thus formed conductive grooves.

Then again formed another pattern in the resist layer ("second pattern in the photoresist layer as the uppermost layer remaining in the multilayer structure, and the remaining layer with a low or ultra-low dielectric constant is again partially travelways with the second pattern in the photoresist layer used as the mask pattern, thereby forming a through hole that communicates with the conductive grooves and a copper interconnect level below. Then the second picture in the layer f�of toresist also removed by ashing in oxygen plasma.

Wired grooves and through holes are then filled with copper, preferably by precipitation, thereby creating a multilayer copper-wire connections.

The substrate for use in these processes can optionally be equipped with a barrier layer (e.g., SiN layer or a SiC layer) as preventing the etching of the layer between the copper layer and the layer with low dielectric constants. In this case, there are formed through holes and grooves, and then, while presented on the substrate, the barrier layer exist as such or after removal of the barrier layer, the photoresist is removed, after which the through holes and conductive grooves are filled with copper.

In the above-described dual process demaskirovanie it could lead to the deposition of silicon resulting from a layer with a low dielectric constant during the etching and ashing in oxygen plasma to form a through connection on the grooves, and this can lead to the formation of the precipitate of silicon on the edges of the grooves. In addition, sedimentation may occur from resists. If these sediments delete them, they can significantly reduce the yield of semiconductor products.

Accordingly, the ashing in oxygen plasma was used to remove patterns in the photoresist layer and etching sludge formed in tra�elements of the relief forming metal wiring. However, the development of imaging technologies ultramicroscope material having a low dielectric constant, i.e. a material with a low dielectric constant must be applied to the insulating layer with low dielectric constants. Currently developed a process of applying a layer with a low dielectric constant having a dielectric constant equal to 3 or less. However, materials with ultralow dielectric will have a low resistance or does not have the resistance to ashing. Therefore, when using materials with a low dielectric constant must be applied in a process that does not include the step of ashing in oxygen plasma after the etching.

For these purposes were developed and described in the prior art so-called wet processes of removal of pickling sludge (post-etch residue removal, PERR).

American patent application US 2003/0148624 A1 describes an arrangement for removing ogolennyh or nesolenyh resists, and these compositions contain Quaternary ammonium hydroxides, such as hydroxide of Tetramethylammonium (TMAN), and organic solvents such as ethanolamine, 1-amino-2-propanol, aminoethoxyethanol, 1-methylaminoethanol, dimethylsulfoxide, N-methylpyrrolidone, IER�of elangligis monomethyl ether or diethylene glycol monobutyl ether. The examples, in particular, describe a composition for removing resist, consisting of 5 wt.% ethanolamine, 50 wt.% of dimethyl sulfoxide, 5 wt.% propylene glycol, 0.05 wt.% TMAN, is at 39.55 wt.% water, and 1 mg/m3or less dissolved oxygen, and a composition for removing resist, consisting of 28 wt.% 1-amino-2-propanol, 62 wt.% N-methylpyrrolidone, 1 wt.% TMAN, 9 wt.% water, and 1 mg/m3dissolved oxygen. These compositions for removing resist of the prior art are used in processes in which the resists should be cleaned using special cleaning compositions containing 1 wt.% or more of hydrogen peroxide and ammonia or ammonium ion.

American patent application US 2004/0106531 A1 and corresponding U.S. patent US 7,250,391 B2 describe compositions for the removal of the resist containing:

(A) a salt of hydrofluoric acid and a base not containing a metal,

(B1) water-soluble organic solvent,

(C) an acid selected from the group consisting of organic acids and inorganic acids, and

(D) the water

as a mandatory component, and

(E) ammonium salt

as an optional component.

Ethanolamine, isopropanolamine, 2-(2-aminoethylamino)ethanol, N-methylethanolamine, N-acylethanolamine, dicyclohexylamine and TMAN can be used as the basis, do not contain�asego metal. Full component (A) preferably used in an amount of from 0.01 to 1 wt.%, based on the weight of the composition for removing resist. In the application, together with difosfonovoy acid () base not containing a metal, can be used in an amount of from 0.1 to 20 wt.%, based on the weight of the composition for removing resist.

Of diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, N-methylpyrrolidone and dimethyl sulfoxide can be used as a water-soluble organic solvent (B).

International patent application WO 2004/100245 A1 describes an arrangement for removing the resist containing H2SiF6and/or HBF4preferably in an amount of from 0.001 to 5% by weight of the composition, an organic solvent preferably in an amount of from 50 to 89% by weight of the composition, optionally an amine, preferably in an amount of less than 1.5% by weight of the composition, the corrosion inhibitor is preferably in an amount of from 0.001 to 10% by weight of the composition, and the rest is water. N-methylpyrrolidone, diethylene glycol monomethyl ether or diethylene glycol monobutyl ether can be used as the organic solvent. Isopropanolamine, 2-(2-aminoethylamino)-ethanol, 2-(2-aminoethoxy)ethanol and ethanolamine can be used as an optional amine. TMAN will apply only in the so-called variant�x with the use of large amounts of water in which practically no organic solvents.

Related U.S. patent application US 2005/0176259 A1 and US 2007/0298619 A1 describe a composition for the removal of the resist containing a Quaternary ammonium hydroxide, for example TMAN, preferably in an amount of from 1 to 20% by weight of the composition, preferably water in an amount of from 5 to 60% by weight of the composition, of water soluble organic solvent, for example dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and water-soluble amine, such as ethanolamine, isopropanolamine, Diethylenetriamine, 2-(2-aminoethoxy)ethanol or N-methylethanolamine, preferably in an amount of from 10 to 50% by weight of the composition. These compositions for removing resist of the prior art are used in the process in which structured before removing the resists should be treated with ozonated water and/or aqueous solution of hydrogen peroxide.

American patent application US 2005/0014667 A1 and the corresponding US patent 7,399,365 B2 describe diluted with water compositions for the removal of the resist containing, for example, from 0.02 to 0.18% by weight of the composition of ammonium fluoride, from 20 to 40% by weight of the composition of water from 59 to 85% by weight of the composition of an amide and an ether solvent, such as, for example, of diethylene glycol monoethyl ether, diethyl�glycol monobutyl ether and N-methylpyrrolidone, from 0.2 to 5% by weight acid, from 0.2 to 5% by weight alkanolamine, such as ethanolamine, isopropanolamine, N-methylethanolamine, or 2-(2-aminoethylamino)-ethanol, and 0.2 to 5% by weight of the composition of Quaternary ammonium compounds, such as, for example, TMAN. These compositions for removing resist of the prior art can be used to remove ogolennyh and nesolenyh resists.

Related U.S. patent application US 2005/0266683 A1 and US 2005/0263743 A1 describe a composition for the removal of the resist containing a Quaternary ammonium hydroxide, for example TMAN, preferably in an amount of from 1 to 30% by weight of the composition, of water, preferably in an amount of from 15 to 94% by weight of the composition, of the organic polar solvent, for example N-methylpyrrolidone, dimethylsulfoxide, 3-amino-1-propanol and ethanolamine, or mixtures thereof, preferably in an amount of from 25 to 85% by weight, and hydroxylamine or a hydroxylamine derivative, preferably in an amount of from 2 to 12% by weight of the composition. Allegedly, it is possible to dispense with the holding stage ashing using oxygen plasma.

American patent application US 2006/0016785 A1 describes aqueous and non-aqueous composition for removing resist, designed to remove ogolennyh or nesolenyh resists, and these compositions contain from 0.5 to 15% by weight of the composition of compound h�termicznego ammonium, for example TMAN or hydroxide of tetrabutylammonium (TWAN), an organic solvent, such as diethylene glycol monomethyl ether or diethylene glycol monobutyl the air.

Example To, in particular, describes a composition for removing resist, consisting of 65 wt.% propylene glycol methyl ether, 39 wt.% propylene glycol propyl ether, 0.4 wt.% water, 0.6 wt.% TWAN, 3 wt.% R-toluensulfonate acid and 1 wt.% ethanolamine. Example L, in particular, describes a composition for removing resist which does not contain water and consisting of 56 wt.% propylene glycol propyl ether, 35.5 wt.% propylene glycol methyl ether, 0.5 wt.% TWAN, 6 wt.% R-toluensulfonate acid and 2 wt.% ethanolamine. Example M, in particular, describes a composition for removing resist, consisting of 91.5 wt.% propylene glycol methyl ether, 0.2 wt.% water. 0.2 wt.% TWAN, 6 wt.% R-toluensulfonate acid and 2 wt.% ethanolamine. In accordance with example C, E, F, J, N, O, A5, R and S, TMAN is used in higher quantities in the range from 2.5 wt.% to 5.5 wt.%. In accordance with the list of abbreviations used in these examples, and PGME, and PGPE should both denote propylene glycol methyl ether. Although it is assumed that PGPE actually stands for propylene glycol propyl ether.

American patent application US 2008/0280452 A1 describes an arrangement for removing neocolony� resists, having a high water content and containing a Quaternary ammonium hydroxide, for example TMAN, TWAN or hydroxide of methyltryptamine (MTRAN) preferably in an amount of from 1 to 20% by weight of the composition, of water soluble organic solvent, for example dimethyl sulfoxide and N-methylpyrrolidone, and water-soluble amine, such as ethanolamine, N-methylethanolamine and 2-(2-aminoethoxy)ethanol, preferably in an amount of from 10 to 15% by weight of the composition. In particular, table 2 describes compositions for the removal of the resist, for example, consisting of 10 wt.% TMAN, 50 wt.% of dimethyl sulfoxide and 40 wt.% water (cleaning solution (G), 5 wt.% TWAN, 30 wt.% N-methylpyrrolidone, 30 wt.% of dimethyl sulfoxide and 25 wt.% water (cleaning solution (J), or 5 wt.% MTRAN, 30 wt.% of dimethyl sulfoxide, 15 wt.% N-methylpyrrolidone, 20 wt.% water and 30 wt.% 2-(2-aminoethoxy)of ethanol. However, for complete removal of resists mandatory pre-treatment with ozonated water and/or aqueous solution of hydrogen peroxide.

Composition for removing resist of the prior art has various flaws and shortcomings.

Thus, the composition for removing resist layer containing N-methylpyrrolidone, concern about the environment, health and safety (EHS).

Composition having a high water content or a high content of Quaternary ammonium hydroxide, can damage materials of low, in particular ultra-low, dielectric constant used in modern technology. In connection with the disposition of hydroxylamine and hydroxylamine derivatives to form complexes and the formation of chelate compounds, compositions containing these compounds, can cause corrosion of copper through-connections and interconnections. Both of these effects can lead to partial or complete failure of the IP.

The intensity of removal of resists, etching sludge (PER) and barrier anti-reflective layer (BARC) in compositions for removing resist layer having a high content of organic solvents strongly depends on the concentration of Quaternary ammonium hydroxides. It is the strong dependence on the concentration makes the optimization of the compositions complex and time-consuming. In particular, you need high concentrations to achieve high removal rates, we again encounter the mentioned unfavorable effects.

Quite often known composition for removing resist showing different intensity of removal for remaining unchanged resists on one side and for PER and BARC. In most cases, PER BARC and more difficult to remove than remaining unchanged resists. This is because PER have than resists chemical nature, � because what BARC are cross-linked materials with a high frequency of cross-links and they are difficult to dissolve or disperse.

Moreover, the composition for removing resist of the prior art can satisfactorily remove the resists, but show poor intensity of removal relative to the etching sludges, which have a complex structure and, among other things, contain material similar to Teflon, and materials containing titanium and/or silicon.

And last but not least, many processes using the composition for removing resist of the prior art, require pre-processing stage before removal. Quite often applied ozonated water and/or aqueous solution of hydrogen peroxide. In addition to concerns about EHS, these strongly oxidizing solutions can damage materials of low or ultra-low dielectric constant, in particular the materials doped with carbon, silicon oxide (storage I / o control), by oxidation of carbon contained in them.

Three-dimensional (3D) technology and structure are becoming more and more important in technology because they can provide the opportunity to further improve system performance, while reducing the size of devices becomes more challenging.

In a three-dimensional� decisions, the photoresists are applied to a relief forming through-connections through the silicon (TSV), and also for the deposition and bar formation conclusions (3D stacked integrated circuits and 3D-SiC; 3D packaging at the level of the plates, 3D-WLP).

Usually positive photoresists thickness of a few micrometers are used for 3D-WLP TSV etching. Usually apply a combination of dry etching of silicon and wet removal of photoresist. In addition, negative photoresists can also be used as a template for the deposition of copper and micro-formation of the bar conclusions. However, the composition for removing resist of the prior art are not always able to remove both negative and positive photoresist in the same manner.

Quite often resists are damaged by the plasma, for example pickling sludge (PER), is very difficult to remove. In order to avoid such PER, requires the additional application of physical force.

For 3D-WLP formation of TSV and micro-formation of the bar of the findings is often carried out on thin silicon wafers mounted on the substrates. In this case, the composition for removing resist layer must be compatible with the adhesive material.

Therefore, it is desirable to have available a composition for removing resist, capable of removing positive and negative photoresists and PER the same, in the most effective manner without damaging the surface layer of the plates, d�jerryh structures plates and adhesive material, connecting a thin silicon wafer with the substrate. However, the composition for removing resist of the prior art cannot or can only partially satisfy these complex requirements.

The objective of the invention

Consequently, the aim of the present invention was to provide new compositions for removing resist and new methods of manufacturing electrical devices using a new composition for the removal of the resist, the compositions and methods do not have to exercise the above drawbacks and disadvantages of prior art.

In particular, new compositions for removal of the resist should no longer contain N-methylpyrrolidone to avoid the problems associated with environmental, health and safety (EHS) caused by the solvent.

New compositions for removing resist no longer needs to show the undesirable effects associated with high content of water and/or a high content of Quaternary ammonium hydroxide, and should no longer cause damage to materials of low, in particular ultra-low, dielectric constant used in modern technology. In addition, new compositions for removing resist no longer needs to contain hydroxylamine and hydroxylamine derivatives, and therefore the risk of cor�Uzziah copper through-connections and interconnections will be reduced or, ideally, be completely excluded.

The intensity of removal of resists, etching sludge (PER) and barrier anti-reflective layer (BARC) in new compositions for the removal of the resist with a high content of organic solvents, more should not depend on the concentration of Quaternary ammonium hydroxides. Thus, optimization and adaptation of new compositions to changes in process parameters must be easily, directly and effectively, so that it was no longer necessary in high concentrations to achieve high removal rates.

New compositions for removal of the resist have to show the same, or substantially the same removal rate for the remaining unchanged resists on one side and for PER BARC and on the other, to the chemical nature and PER BARC no longer impede the effective deletion.

Moreover, a new composition for the removal of the resist must not only remove the resists, but also to demonstrate excellent intensity of removal in relation to PER, which have a complex structure and contain material similar to Teflon, and materials containing titanium and/or silicon.

New ways of manufacturing electrical devices, particularly semiconductor integrated circuits (IC), liquid crystal display panels, orga�quarter electroluminescent display panel, micromachines, DNA chips and micro plants, mainly used used in new compositions for removal of the resist, should no longer require pre-processing stage before removal. In particular, it is necessary to completely eliminate the use of ozonated water and/or aqueous solution of hydrogen peroxide to related concerns about EHS and order to avoid damage of materials with low and ultra-low dielectric constant caused by these highly oxidizing solutions. In General, new methods of production must ensure that electrical devices that are completely or essentially do not contain defects, exhibit excellent functional properties and have a long service life.

Last but not least, a new composition for the removal of the resist should preferably be applied to 3D technologies for the fabrication of 3D structures, in particular in the field of pattern formation through-connections through the silicon (TSV), as well as for deposition and bar formation conclusions (3D stacked integrated circuits and 3D-SiC; 3D packaging at the level of the plates, 3D-WLP). In these applications they should be able to remove the positive and negative photoresists and PER the same, the most beneficial Abrazame damage the surface layers of the plates, relief structures of the plates and the adhesive material connecting the thin silicon wafer with the substrate.

Summary of the invention

Accordingly, he discovered a new liquid composition, wherein said composition does not contain N-alkylpyridine, hydroxylamine and hydroxylamine derivatives, has a dynamic shear viscosity at 50°C from 1 to 10 MPa·s, measured by rotational viscometry, and contains, based on the total weight of the composition, (A) from 40 to 99.95 wt.%, based on the total weight of the composition, of at least one polar organic solvent selected from the group consisting of solvents exhibiting in the presence of from 0.06 to 4 wt.% dissolved hydroxide of Tetramethylammonium (In), mass fraction of which is taken, based on the total weight of the respective test solution (AB), a constant intensity of removal at 50°C for polymeric barrier anti-reflective layer thickness of 30 nm containing chromophoric groups that absorb in the far UV radiation,

(B) from 0.05 to <0.5 wt.%, based on the total weight of the composition, of at least one Quaternary ammonium hydroxide, and

(C) <5 wt.%, based on the total weight of the composition, of water.

Further, in the description of a new liquid composition that does not contain N-alkylpyridine, hydroxylamine and hydroxylamine derivatives and Dean has�dynamic shear viscosity at 50°C from 1 to 10 MPa·s, measured by rotational viscometry, referred to as "the composition or compositions of the invention" depending on the context.

In addition, a new method for producing a liquid composition containing N-alkylpyridine, hydroxylamine and hydroxylamine derivatives, contains the following stages:

I. choose at least one polar organic solvent (A), demonstrating the presence of from 0.06 to 4 wt.% dissolved hydroxide of Tetramethylammonium (In), mass fraction of which is taken, based on the total weight of the respective test solution (AB), a constant intensity of removal at 50°C for polymeric barrier anti-reflective layer thickness of 30 nm containing chromophoric groups that absorb in the far UV radiation,

II. mixing, based on the total weight of the mixture,

(A) from 40 to 99.95 wt.% at least one selected from polar organic solvents

(B) from 0.05 to <0.5 wt.% at least one Quaternary ammonium hydroxide, and

(C) <5 wt.% water,

in the absence of N-alkylpyridine, hydroxylamine and hydroxylamine derivatives, and

III. bring the dynamic shear viscosity at 50°C the mixture obtained at stage (II) of the process, to a value of from 1 to 10 MPa·s, measured by rotational viscometry.

Further, in the description of a new method of obtaining the Jew�Oh songs, not containing N-alkylpyridine, hydroxylamine and hydroxylamine derivatives, referred to as a "delivery method of the invention."

Moreover, he discovered a new method of manufacturing electric devices, and said method includes the stage of:

1) applying an insulating dielectric layer consisting of at least one material with a low or ultra-low dielectric constant on the substrate surface,

2) applying a positive or negative of the resist layer on the surface of the insulating dielectric layer (1),

3) exposure of the resist layer to selective exposure to electromagnetic radiation or corpuscular radiation,

4) the manifestation of the resist layer (3) for the formation of the pattern in the resist.

5) dry etching the insulating dielectric layer (1) using the pattern in the resist (4) as a mask for formation of conductive grooves and/or through holes communicating with the surface of the substrate,

6) selecting at least one polar organic solvent (A) exhibiting in the presence of from 0.06 to 4 wt.% dissolved hydroxide of Tetramethylammonium (In), mass fraction of which is taken, based on the total weight of the respective test solution (AB), a constant intensity of removal at 50°C polymeric barrier anti-reflective layers tol�other 30 nm, containing chromophoric groups that absorb in the far UV radiation,

7) providing at least one composition for the removal of the resist that does not contain N-alkylpyridine, hydroxylamine and hydroxylamine derivatives and having a dynamic shear viscosity at 50°C from 1 to 10 MPa·s, measured by rotational viscometry and comprising based on the total weight of the composition,

(A) from 40 to 99.95% of at least one polar organic solvent selected in accordance with stage (6) the process

(B) from 0.05 to <0.5 wt.%, based on the total weight of the composition, of at least one Quaternary ammonium hydroxide, and

(C) <5% by weight, based on the total weight of the composition, of water,

8) removal of the pattern in the resist layer and the etching sludge using the wet process using at least one composition for the removal of the resist obtained in accordance with stage (7) of the process, and

9) filling conductive grooves and through holes of at least one material having low electric resistance.

Further, in the description of a new method of manufacturing electronic devices referred to as "manufacturing method of the invention."

In addition, it was discovered a new use of liquid compositions for the removal of negative and positive photoresists and etching sludge in the production of 3 stacked integrated circuits and 3D packaging at the level of the plates by forming relief through-connections through the silicon and/or by deposition and bar formation conclusions moreover, the specified liquid composition does not contain N-alkylpyridine, hydroxylamine and hydroxylamine derivatives, has a dynamic shear viscosity at 50°C from 1 to 10 MPa·s, measured by rotational viscometry and contains, based on the total weight of the composition,

(A) from 40 to 99.95 wt.%, based on the total weight of the composition, of at least one polar organic solvent selected from the group consisting of solvents exhibiting in the presence of from 0.06 to 4 wt.% dissolved hydroxide of Tetramethylammonium (In), mass fraction of which is taken, based on the total weight of the respective test solution (AB), a constant intensity of removal at 50°C polymeric barrier anti-reflective layer thickness of 30 nm containing chromophoric groups that absorb in the far UV radiation,

(B) from 0.05 to <0.5 wt.%, based on the total weight of the composition, of at least one Quaternary ammonium hydroxide, and

(C) <5 wt.%, based on the total weight of the composition, of water.

Further, in the description of a new use of liquid compositions referred to as "the application of the invention."

Advantages of the invention

Whereas the prior art discussed above, for specialists in the art was a surprise that the purposes underlying the present invention, can be achieved a CR� care compositions of the invention, obtain of the invention and the manufacturing method of the invention.

In particular, the compositions of the invention no longer contains N-alkylpyridine, in particular, N-methylpyrrolidone, so no problems with environmental, health and safety (EHS) related thereto.

The compositions of the invention already showed adverse effects associated with high water content and/or high content of Quaternary ammonium hydroxide, and could not damage the materials of low, in particular ultra-low, dielectric constant used in modern technology. In addition, the compositions of the invention did not contain hydroxylamine and hydroxylamine derivatives, so that the risk of corrosion of copper through-connections and interconnections was considerably reduced or, in many cases, completely eliminated.

In the concentration ranges from 0.06 to 4% by weight of the composition of the invention, the intensity of removal of resists, etching sludge (PER) and barrier anti-reflective layer (BARC) in compositions of the invention longer dependent on the concentration of Quaternary ammonium hydroxides. Thus, optimization and adaptation of the compositions of the invention to changes in process parameters was carried out easily, directly and effectively, so that it was no longer necessary in high concentrations for the achievement�of high removal rates.

The compositions of the invention showed equal or essentially equal intensity of removal for remaining unchanged resists on one side and for PER BARC and the other to the different chemical nature and PER BARC is no longer a barrier to their effective removal.

Moreover, the compositions of the invention are not only excellent removed the resists, but also showed excellent removal rate relative to PER, which have a complex structure and contain material similar to Teflon, and materials containing titanium and/or silicon.

In General, the compositions of the invention can be stored, transported and used without the occurrence of problems associated with environmental, health and safety (EHS).

The delivery method of the invention can be carried out in a simple, economical, safe and perfectly repeatable manner without the occurrence of problems with EHS, and did not need to be special and special tools and precautions. Method provided liquid compositions, especially compositions of the invention, possessing excellent application profiles and profile properties.

The manufacturing method of the invention for electrical devices, particularly semiconductor integrated circuits (IC), liquid crystal display panels, organic electrolumines�/ display panels and printed circuit boards, micromachines, DNA chips and micro plants, mainly used, no longer needed in pre-processing stage before removal. In particular, it was possible to completely stop the use of ozonated water and/or aqueous solution of hydrogen peroxide to related concerns about EHS and it was possible to completely eliminate the damage of materials with low or ultra-low dielectric constant of these strongly oxidizing solutions. In General, the method of manufacture of the invention, provided an electrical device that are completely or essentially do not contain defects, exhibit excellent functional properties and have a long service life.

Moreover, the compositions of the invention is best suited for the application of the invention in a 3D technology for the fabrication of 3D structures, in particular in the field of pattern formation through-connections through the silicon (TSV), as well as for deposition and bar formation conclusions (3D stacked integrated circuits and 3D-SiC; 3D packaging at the level of the plates, 3D-WLP). In these applications they were able to remove the positive and negative photoresists and PER very quickly, it is the same in the most effective manner without damaging the surface layer of the plates, relief structures plates and adhesive material connecting t�ncie silicon wafer with the substrate.

Detailed description of the invention

In the broadest sense, the present invention relates to liquid compositions that do not contain N-alkylpyridine, in particular N-methylpyrrolidone and N-ethylpyrrolidin and hydroxylamine and hydroxylamine derivatives, in particular derivatives of hydroxylamine as described in the American patent applications US 2005/0266683 A1, page 4, paragraphs [N], and US 2005/0263743 A1, page 4, paragraph [0057] to page 5, paragraph [0063].

In the context of the invention description of the "liquid" means that the composition of the invention is liquid at least at room temperature (i.e. 23°C), preferably at at least 0°C, and most preferably at least -10°C.

Moreover, in the context of the invention the characteristic of "not containing" means that the relevant compounds cannot be detected in the composition of the invention with the help of the most famous modern analytical methods qualitative and/or quantitative detection of N-alkylpyridine, hydroxylamine and hydroxylamine derivatives, for example using gas chromatography and/or mass spectrometry.

The composition of the invention demonstrates a dynamic shear viscosity at 50°C, measured by rotational viscometry, from 1 to 10 MPa·s, preferably from 2 to 8 MPa·s, more preferably from 1.5 to 7 MPa·s and most�e preferably from 2 to 6 MPa·s. Preferably the composition of the invention also demonstrates the dynamic shear viscosity at 23°C, measured by rotational viscometry, from 2 to 20 MPa·s, more preferably from 3 to 16 MPa·s and most preferably from 3 to 14 MPa·s.

The composition of the invention may be a dispersion, i.e. an emulsion or a suspension or a homogeneous composition, where all the components are dispersed at the molecular level. Preferably the composition of the invention is a homogeneous, dispersed at the molecular level composition.

The composition of the invention contains, based on the total weight of the composition, from 40 wt.%, preferably from 45 wt.% and most preferably from 50 wt.% up to 99.95 wt.% or more preferably up to 99.94 wt.% at least one polar organic solvent (A). The polar organic solvent may be aprotic or proton.

A polar organic solvent (A) is selected from the group consisting of solvents, which display in the presence of dissolved hydroxide of Tetramethylammonium (B) in an amount of from 0.06 to 4 wt.%, based on the total weight of the respective test solution (AB), at 50°C constant the intensity of removal of polymeric anti-reflective barrier layer of a thickness of 30 nm containing chromophoric groups that absorb in the far UV radiation.

Product�erotica "constant" means, that in this range the intensity of the removal wholly or almost not dependent on the concentration of the hydroxide of Tetramethylammonium ().

In order to measure the intensity of removal of polymeric barrier anti-reflective layer preferably is applied to the semiconductor wafer surface. Then the barrier anti-reflective layer on the surface of the semiconductor wafer is exposed to the test solution (AB) hydroxide of Tetramethylammonium (b) In polar organic solvent (A), which can be tested at different concentrations (B).

Preferably, the hydroxide of Tetramethylammonium (In) is added in the form of an aqueous solution containing, based on the total weight of the aqueous solution, 25 wt.% hydroxide of Tetramethylammonium (In). Thus, the test solution (AB) may contain, based on total weight of the test solution, up to 16 wt.% water (C).

Preferably, the test solution (AB) are mixed during the tests with a constant speed of rotation, more preferably at from 50 to 200 rpm, even more preferably at 75 to 125 rpm and most preferably at 100 rpm.

In all tests the barrier anti-reflective layers on the surfaces of semiconductor wafers are simultaneously exposed to the test solution (AB). Preferably, the length in�action is 180 sec.

After exposure of part of the semiconductor wafer load-bearing barrier anti-reflective layers are removed from the test solution (AB), washed with a polar organic solvent, preferably isopropanol, and then with deionized water, and dried with dry chemically inactive gas, preferably nitrogen. Most preferably, the washing stage and drying are carried out at moderate temperatures, preferably at temperatures from 23 to 50°C.

After the drying phase, the investigation known traditional spectroscopic methods to identify whether there are still barrier anti-reflective layers. Preferably used for this purpose is infrared spectroscopy with Fourier transform (Fourier Transformation IR Spectroscopy, FTIR).

If the barrier anti-reflective layers are still present, their thickness is measured by known conventional methods of measuring the thickness of thin layers. Preferably used for this purpose is infrared spectroscopy with Fourier transform (FTIR) and/or interferometry.

Most preferably, the barrier anti-reflective layers are completely removed during the interaction with the test solution (AB).

For sample tests described above, any known polymer composition antireflection coatings, for example, described in U.S. patent US 5,919,599, from �of column 3, line 40 to column 16, line 36, and from column 17, line 25 to column 18, line 25, in combination with Figure 1, can be used to prepare polymeric barrier anti-reflective layers containing chromophoric groups that absorb in the far UV radiation.

As is known in the art, due to their polymeric and cross-linked nature, the barrier anti-reflective layers is much more difficult to remove than structured resists this random tests ensure that the organic polar solvents (A) are selected such that the composition of the invention is more fully able to remove structured resists and etching sludge together with the barrier anti-reflective layers, most preferably within 180 sec, without or essentially without re-deposition.

Preferably polar organic solvents (A) have a boiling point at atmospheric pressure above 100°C, more preferably above 120°C and most preferably above 150°C.

More preferably, the polar organic solvents (A) have flash points measured in a closed crucible, above 50°C, more preferably above 55°C and most preferably above 60°C.

Most preferably the polar organic solvent (A) is selected from the group consisting of aliphatics�x polyamines, containing at least two simplest amino group, aliphatic alkanolamines containing at one carbon chain of at least 3 carbon atoms between the amino group of one simple and one hydroxyl group, aliphatic sulfoxides and N-substituted imidazolov. In particular, the solvent (A) is selected from the group consisting of Diethylenetriamine (boiling point 207°C, flash point 102°C), N-methyl imidazole (boiling point 198°C, flash point 92°C), 3-amino-1-propanol (boiling point 187°C, flash point 101°C), 5-amino-1-pentothal (boiling point 222°C, flash point 65°C) and dimethyl sulfoxide (boiling point 189°C, flash point 87°C).

The composition of the invention contains, based on the total weight of the composition, from 0.05 to <0.5 wt.%, preferably from 0.06 to <0.5 wt.% at least one Quaternary ammonium hydroxide.

Preferably, the Quaternary ammonium hydroxide (B) is selected from the group consisting of hydroxides of Tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, benzyltrimethylammonium, and (2-hydroxyethyl)ammonium, in particular the hydroxide of Tetramethylammonium.

Furthermore, the composition of the invention contains, based on the total weight of the composition of the invention, <5 wt.%, preferably <4 wt.%, more preferably <3 wt.% and most p�edocfile < 2 wt.% water. The water content can be so low that it will not be detected is known and generally accepted methods qualitative and quantitative determination of water.

The composition of the invention may also contain at least one additional component selected from the group consisting of polar organic solvents (D) than that of the solvent (A), corrosion inhibitors (E), chelating agents (F), fluoride salts (G) and surfactant (N).

Preferably the polar organic solvent (D) is selected from the group of solvents, demonstrating the presence of from 0.06 to 4 wt.% dissolved hydroxide of Tetramethylammonium (In), mass fraction of which is taken, based on the total weight of the test solution (DB), the removal rate at 50°C for polymeric barrier anti-reflective layer thickness of 30 nm containing chromophoric groups that absorb in the far UV radiation, which increases with increasing the concentration of hydroxide of Tetramethylammonium.

Also here, the hydroxide of Tetramethylammonium (B) is preferably added in the form of an aqueous solution containing, based on the total weight of the aqueous solution, 25 wt.% hydroxide of Tetramethylammonium (In). Thus, the test solutions (DB) can contain, based on total weight of the test solution, up to 16 wt.% water (C)./p>

Removal rates of the test solutions (DB) defined in the same way as described above for the test solution (AB).

Preferably, the intensity of removal of the test solutions (DB) ranging from 0 nm to 100 nm under the conditions specified above at a concentration of 1 wt.% hydroxide of Tetramethylammonium, based on the total weight of the test solution (DB).

Preferably polar organic solvents (D) have a boiling point at atmospheric pressure above 100°C, more preferably above 120°C and most preferably above 150°C.

More preferably, the polar organic solvents have flash points measured in a closed crucible, above 50°C, more preferably above 55°C and most preferably above 60°C.

Most preferably the polar organic solvent (D) is selected from the group consisting of alkanolamines, alkalophiles monoalkyl esters, N-substituted piperidines, N-substituted cyclic ureas and N-substituted imidazolov, in particular ethanolamine (boiling point 172°C flash point 85°C), N-methylethanolamine (boiling point 160°C, flash point 72°C), N-acylethanolamine (boiling point 168°C, flash point 78°C), isopropanolamine (boiling point 159°C flash point 71°C), 2-(2-aminoethylamino)ethanol (boiling point 243°C, accuracy�and ignition 144°C), 2-(2-aminoethoxy)ethanol (boiling point 223-242°C, flash point 127°C), of diethylene glycol monoethyl ether (boiling point 193°C, flash point 93°C), diethylene glycol monobutyl ether (boiling point 230°C, flash point 107°C), N-(2-hydroxyethyl)piperidine (boiling point 198-203°C, flash point 83°C) 1,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidinone (boiling point 246°C flash point 121°C), N-(3-aminopropyl) - imidazole (boiling point 296°C, flash point 154°C), and dicyclohexylamine (boiling point 256°C, flash point 105°C).

The concentration of the polar solvent (D) in the compositions of the invention can vary greatly. However, the concentration must be so high that the organic polar solvent (A) is mainly used CharacterIterator profile of properties of the compositions of the invention. Preferably the weight ratio of the polar organic solvent (A) and polar organic solvent (B) is in the range from 2:1 to 1:2, more preferably from 1.5:1 to 1:1.5 and most preferably from 1.2:1 to 1:1.2.

In principle, it is possible to use any known corrosion inhibitor (E) for metals. Preferably, the corrosion inhibitor is selected from the group consisting of copper corrosion inhibitors (E), as described for example in:

international patent application WO 2004/100245 A1, with �Tr.9, paragraph [0030] to page 10, paragraph [0031],

American patent application US 2005/0176259 A1, page 4, paragraph [0049] to page 5, paragraph [0059],

American patent application US 2005/0263743 A1, page 5, paragraph [0067] to page 6, paragraph [0073], and

American patent application US 2008/0280452 A1, page 3, paragraph [0045] to page 4, paragraph [0053].

Copper corrosion inhibitors (E) can be used in highly variable quantities. Preferably they are used in conventional and effective amounts, as described in the above prior art.

In principle, any known chelating agent (F) may be used in compositions of the invention. Preferably the chelating agent (F) is selected from the group of copper chelating agents (F), in particular from the group of copper chelating agents (F) are described, for example, in U.S. patent applications

- US 2004/0106531 A1, page 6, paragraph [0074],

- US 2005/0263743 A1, page 5, paragraph [0070] to page 6, paragraph [0073] in conjunction with the paragraph [0078].

Quite often, these copper hepatoblastoma substance (F) are also used as copper corrosion inhibitors (E).

Copper hepatoblastoma substance (F) can be used in various amounts. Preferably they are used in conventional and effective amounts, as described in the above prior art.

In principle, any known fluoride salt (G) may �be used in the compositions of the invention. Preferably, the fluoride salt (G) is selected from the group of salts of hydrofluoric acid and a base not containing a metal, as described in American patent application US 2004/0106531 A1, page 3, paragraphs [0035] to [0041]. Fluoride salt (G) can be used in various amounts. Preferably they are used in conventional and effective amounts, as described in the above prior art, in particular in paragraph [0041].

In principle, any known surface-active agent (N) can be used in the compositions of the invention. Preferably, the surfactant (H) is selected from the group of surfactants (N) described in the American patent application US 2008/0280452 A1, page 4, paragraph [0054] to page 5, paragraph [0061]. Surfactant (N) can be used in various amounts. Preferably they are used in conventional and effective amounts, as described in the above-mentioned prior art, in particular in paragraph [0061].

The compositions of the invention can be obtained in various ways. Preferably they are obtained in accordance with the method of producing the invention. The advantage of this invention is that the delivery method of the invention can also be applied for other compositions that are different from the compositions of the invention.

In the first stage of the method for the preparation�Oia invention, at least one polar organic solvent (A) is chosen as described above.

In the second stage, the production method of the invention

(A) from 40 wt.%, preferably from 45 wt.% and most preferably from 50 wt.% up to 99.95 wt.% or more preferably up to 99.94 wt.% at least one selected from polar organic solvents

(B) from 0.05% or more preferably from 0.6 wt.% to <0.5 wt.% at least one Quaternary ammonium hydroxide, as disclosed above, and

(C) <5 wt.%, preferably <4 wt.%, more preferably <3 wt.% and most preferably <2 wt.% water,

each mass fraction is taken, based on the total weight of the composition and, in particular, compositions of the invention.

At least one additional component selected from the group consisting of polar organic solvents (D) than that of the solvent (A), corrosion inhibitors (E), chelating agents (F), fluoride salts (G) and surfactant (N), described above, may be added in the first stage of the process or individual stages, preferably in amounts described in the above prior art.

For the production method of the invention it is important that the above components were mixed with each other in the absence of N-alkylpyridine, hydroxylamine and hydroxylamine derivatives as described above.

In the third stage of the method the floor�display of the invention, the shear viscosity at 50°C the mixture obtained in the second stage of the process is brought to 1 to 10 MPa·s, preferably from 2 to 8 MPa·s, more preferably from 1.5 to 7 MPa·s and most preferably from 2 to 6 MPa·s.

Stage of the process can be carried out in a separate stage or it can be included in each of the other stages in the production method of the invention. The last stage can be done by carefully selecting the components for the second stage of the process so that the resulting mixture has already demonstrated the necessary dynamic viscosity.

Most preferably the composition of the invention also demonstrates the dynamic shear viscosity at 23°C, measured by rotational viscometry, from 2 to 20 MPa·s, more preferably from 3 to 16 MPa·s and most preferably from 3 to 14 MPa·s.

Common and standard mixing processes and mixing, such as cameras with mechanical stirring, in-line apparatus for dissolution, the impellers with a large shear force, ultrasonic mixers, homogenizing head or counterflow mixers, can be used to mix the components of the compositions, in particular compositions of the invention.

The compositions of the invention, the composition obtained in accordance with the method of producing the invention and most preferably, compositions of the invent�tion, obtained in accordance with the method of producing the invention, can be used for different purposes. In particular, they are used in the manufacturing method of the invention.

The manufacturing method of the invention ensures obtaining the most preferred electrical devices, particularly semiconductor integrated circuits (IC), liquid crystal display panels, organic electroluminescent display panels, printed circuit boards, micro machines, DNA chips and micro plants, but mostly IP with LSI or VLSI.

The manufacturing method of the invention includes the step of applying an insulating dielectric layer comprising at least one material with a low or ultra-low dielectric constant on the surface of the substrate on the first stage of the process.

Suitable materials with low or ultra-low dielectric constant and suitable methods for obtaining the insulating dielectric layers are described, for example, in U.S. patent applications US 2005/0176259 A1, page 2, paragraphs [0025] to[0027], US 2005/0014667 A1, page 1, paragraph [0003], US 2005/0266683 A1, page 1, paragraph [0003] and page 2, paragraph [0024] or US 2008/0280452 A1, paragraphs [0024] to[0026], or in the American patent US 7,250,391 B2, column 1, lines 49 to 54.

Suitable substrates, especially semiconductor substrates, typically used in the manufacture of ICS, such as Samsung GA�p silicon wafers.

In the second stage of the process is applied a positive or negative resist layer on the surface of the insulating dielectric layer.

Suitable materials and methods for producing the positive and negative layers of the resist is described, for example, in U.S. patent US 7,250,391 B2, column 1, lines 55 to 60, or in the American patent applications US 2005/0176259 A1, page 2, paragraphs [0029] and [0030], US 2006/0016785 A1, page 3, paragraphs [0025] to[0027], or US 2008/0280452 A1, paragraphs [0027] to[0029] and page 5, paragraph [0062].

In the third stage, the resist layer is selectively exposed to electromagnetic radiation or corpuscular radiation.

Preferably the electromagnetic radiation applied UV rays, far ultraviolet rays, excimer laser beams, in particular KrF-, ArF -, or F2-excimer laser beams, or x-rays. To exposure the resist layer may be subjected to exposure to a light source capable of emitting active rays, such as a mercury lamp, low pressure mercury lamps high pressure mercury ultra high pressure lamp or a xenon lamp, through a desired mask pattern.

The resist layer may also be directly subjected to corpuscular radiation, preferably electron beams.

Then, if desired, the pattern in the resist can be further dried (drying after irradiation).

In the fourth stage about�of essa selectively exposed to radiation, the resist layer exhibit with developing solution, preferably the aqueous alkaline solution, as described, for example, in U.S. patent application US 2008/0280452 A1, page 5, paragraph [0062], to form a pattern in the resist.

At the fifth stage of the process the insulating dielectric layer is etched by the dry method with the use of the pattern in the resist layer as a mask for forming the conductive grooves and/or through holes communicating with the surface layer, located below, as, for example, with the surface of the substrate, with the surface of the wiring level below, where the transaction comprises at least one material having a low electrical resistance, in particular copper or copper alloy, or with the surface of the etching blocking layer, for example a layer of silicon oxide nitride, is placed between the surface below and an insulating dielectric layer, which is subject to dry etching. Preferably as an agent for dry-etching is applied fluorine-containing plasma, in particular on the basis of fluorocarbon gas.

During the stage of dry etching are formed by etching sludge that must be removed during the fabrication stage (back-end of the line, BEOL) process of manufacturing electrical devices. These pickling sludge may have different compositions and contain materials similar to Teflon, and materials containing t�tan and/or silicon.

In the sixth stage of the process, at least one polar organic solvent (A) is selected, as described above.

On the seventh stage of the process, at least one polar organic solvent (A) used to produce at least one composition of the invention as a composition for removing resists as described above.

On the eighth stage of the process to remove the pattern in the resist and etching and wet sludge is applied at least one composition for the removal of the resist obtained in accordance with the seventh stage of the process.

The efficiency of the removal process of the resist (the eighth stage) can be improved by irradiating a solution to remove the resist by ultrasound.

Preferably the eighth stage of the process is carried out at temperatures from 0 to 70°C, more preferably from 10 to 65°C and most preferably from 50 to 60°C.

One of the main advantages of the manufacturing method of the invention is that through the use of the composition for removing resist of the invention, may be excluded ashing stage, in particular the stage of the ashing with the use of plasma containing oxygen, or preliminary stage of purification, in particular preliminary stage of purification using ozone water or hydrogen peroxide. Moreover, there is about�the absence or very weak re-deposition of the cured particles of the resist and/or etching sludge.

After removal of the pattern in the resist layer and the etching sludge obtained conductive structure of the grooves and/or through holes may be washed, in particular deionized water, to remove any residue compositions for the removal of the resist. Then, the resulting structure can be dried preferably dry chemically inactive gas, in particular nitrogen.

The ninth stage of the process wired grooves and through holes are filled by at least one material having low electric resistance. To this end preferably used copper or alloys of copper, most preferably copper. Preferably can be used known solutions for copper deposition and the deposition methods described, for example, in U.S. patent application US 2006/0213780 A1.

In the manufacturing process of the invention can be applied to the layer of hard mask, as described, for example, in American patents US 6,074,946 or US 6,218,078 B1 or in the American patent applications US 2008/0286977 A1, US 2008/10305441 A1, US 008/0305625 A1 or US 2009/0035944 A1. Said layer of hard mask is selectively etched at the fifth stage of the process, using the pattern in the resist layer from the fourth stage of the process as a mask.

Alternatively, the barrier anti-reflective layer, such as described in U.S. patent US 5,919,599, can be placed �between the resist layer and the insulating dielectric layer. Additionally, the barrier anti-reflective layer can also be placed between the layer of hard mask and a resist layer. In both cases, the barrier anti-reflective layer is selectively etched at the fifth stage of the process, using the pattern in the resist layer from the fourth stage of the process as a mask.

After carrying out the manufacturing process of the invention, the surface can be polished by methods and equipment for chemical-mechanical polishing (CMP), which are widely known in the field of manufacturing electrical devices, such as IP. Then another layer of dielectric material with low dielectric constant is not necessarily another layer hard mask, another optional barrier anti-reflective layer, and definitely another resist layer can be applied when repeated process of manufacture of the invention.

An electrical device received in accordance with the manufacturing method of the invention, have excellent functional properties and a very long service life.

One of the unexpected advantages of the compositions of the invention that due to the high boiling point of the used organic polar solvents (A) and an optional polar organic solvent (D), they all exhibit a low vapor pressure at moderate temperatures�x, in particular in the temperature range from room temperature to 100°C. moreover, due to the high points of ignition used organic polar solvents (A) and an optional polar organic solvent (D) all of the compositions of the invention are non-combustible and easily flammable. And last but not least, organic polar solvents (A) and the optional organic solvent (D) is not critical to the ESH. Therefore, it is equally applicable to the compositions of the invention in which they are contained. Thus, the compositions of the invention can be obtained, stored, transported, applied and disposed of without any problem with ESH.

Equally unexpected advantage of the compositions of the invention is that it is very suitable for application of the invention.

According to the application of the invention composition of the invention is used to remove positive and negative resists, and PER with covered plates and structured plates, usually used for the manufacture of 3D architectures of IP, denoted by 3D-SiC 3D-WLP. In these 3D architectures of IP interconnects are fabricated by forming relief through-connections through the silicon by deposition and by forming the bar of the findings (see also Scientific Report 2008, Advanced Packaging and 3D Interconnect Interconnect and Packaging, 3D Stacked 1C (3D-SIC), 3D-WLP: Micro-Bumping).

According to the application of the invention composition of the invention is used to remove photoresists and PER with covered and structured wafers using known and conventional methods and equipment. After removal of the photoresists of the wafers are rinsed and dried. Success removing step, i.e. the complete absence of photoresists and PER, can be confirmed by optical and scanning electron microscopy (X-SEM), atomic force microscopy (AFM) and infrared spectroscopy with Fourier transform (FTIR).

Compatibility of the composition of the invention with an adhesive material connecting the thin plate with the substrate, i.e., the presence of an intact adhesive material, can be confirmed via the same methods.

Most unexpectedly, that the composition of the invention has the ability to remove the positive and negative photoresists and PER with covered and embossed plates quickly and completely without damaging the delicate structures of the embossed plates or the presence of the adhesive material.

Examples and comparative experiments

Example 1

The choice of polar organic solvents (A)

Polar organic solvents, are presented in Table 1, were pre-selected according to their cleansing options and also their high boiling points, high points of ignition and ratings EHS (i.e. RA�toricelli should cause the least possible problems related EHS) of polar organic solvent (S) from the group consisting of chlorides, CHLOROFORMATES, alcohols, diols, polyols, aldehydes, acetals, ketones, amines, amino alcohols, carboxylic acids and derivatives, heterocyclic compounds, ionic liquids, NITRILES, urea derivatives, vinyl compounds, vinyl ethers and aliphatic amides.

Table 1
Preliminary selection of polar organic solvents
Code of solventSolventBoiling point/°CFlash point (closed Cup)/°C
S1Diethylenetriamine207102
S2N-methylimidazole19892
S33-amino-1-propanol187101
S422265
S5dimethyl sulfoxide18987
S6N-(3-aminopropyl)imidazole296154
S72-(2-aminoethoxy)ethanol223-242127
S8N-acylethanolamine16878
S9N-methylethanolamine16072
S10Ethanolamine17285
S11Isopropanolamine15971
S122-(2-aminoethylamino)ethanol243144
S13N-(2-hydroxyethyl)piperidine198-20383
S141,3-dimethyl-3,4,5,6-tetrahydro-(1H)-pyrimidinone242121
S15Of diethylene glycol monobutyl ether230107
S16Of diethylene glycol monoethyl ether19393
S17Dicyclohexylamine256105

For the final selection of the solvents (A) small samples of silicon semiconductor wafers were coated with a polymeric barrier anti-reflective layers with a thickness of 30 nm containing chromophoric groups that absorb in the far UV. Polymeric barrier anti-reflective layers were cross-linked.

Then received the test solutions of hydroxide of Tetramethylammonium (TMAN) (B) in each of the solvents (S), are presented in Table 1. Every batch of test solutions (SB) consisted of seven races�thieves with concentrations TMAN 0.06, 0.1, 0.2, 0.5, 1.0, 2.0 and 4 wt.%, where the mass fraction is taken, based on the total weight of the respective test solution (SB), by adding appropriate amount of an aqueous solution containing 25 wt.% TMAN.

The intensity of removal of each of the test solutions (SB) of each series was defined as follows.

Covered portion of the silicon semiconductor wafer was exposed in a beaker at 50°C for 180 sec step test solution, which was stirred at a speed of 100 rpm Then covered a portion of the silicon semiconductor wafer was removed from the test solution (SB), washed with isopropanol, then with deionized water and dried at 50°C by a stream of dry nitrogen. After cooling to room temperature was studied by the method of IR-spectroscopy with Fourier transform and the method of interferometry on the subject of whether there is still, and if so, at what thickness, cross-linked polymeric barrier anti-reflective layer.

Table 2 gives an overview of the results obtained.

/tr>
Table 2
The choice of polar organic solvents (A)
Code will dissolve�La The intensity of removal:
nm deleted by the corresponding percentage by weight TMAN:
0.060.10.20.51.02.04.0
S130303030303030
S230303030303030
S330303030303030
S430303030303030
S530303030303030
S6000007.530
S7000003030
S8000007.530
S9000001730
S100000 21630
S11000091630
S12000042030
S13000051530
S14000013030
S15000041530
S1600 000630
S170000231530

The test results presented in Table 2 show that only the intensity of removal from solutions S1, S2, S3, S4 and S5 did not depend on the concentration of TMAN and that complete removal of the crosslinked polymeric barrier anti-reflective layers can be achieved with such low concentrations, 0.06 wt.%, based on the total weight of the respective test solution. Therefore, only solutions S1, S2, S3, S4 and S5 are suitable as polar organic solvents (A) for use according to the invention. The other tested solvents (S) suitable only as an optional polar organic solvent (D).

Example 2

The effect of the concentration TMAN in the test solutions (SB) on the intensity of etching

In addition, the compatibility of the test solutions (SB) containing polar organic solvents of Table 1 and 1 wt.%, 2 wt.% and 4 wt.% TMAN, where the mass fraction is taken, based on the total weight of the respective test�solution, was tested, as described next.

Samples of silicon semiconductor wafers were covered with layers of ultra-low dielectric constant thickness of 400 nm, consisting of doped carbon silicon oxide (Black Diamond™, manufactured by Applied Materials, Inc.).

In order to assess the impact of the test solutions (SB) layers with a low dielectric constant raw layer with a low dielectric annealed at 150°C for 120 min as a reference. In this case, the annealing caused only minimal changes in thickness and refractive index.

Samples of silicon wafers covered with a layer with a low dielectric constant, and then was subjected to a stirred (100 rpm) of the test solutions (SB) in a beaker at 50°C for 180 seconds. Then the samples were want to come out of the test solutions (SB), washed with isopropanol and water and then dried in a stream of dry nitrogen at 50°C. After cooling to room temperature was measured by changing the thickness of layers with a low dielectric constant and changes in the refractive index.

In contrast to the untreated layer with a low dielectric constant almost all exposed layers with ultra-low dielectric ol�the permittivity showed a significant reduction in thickness, in particular, the layers that were exposed to test solutions (SB) containing 2 wt.% and 4 wt.% TMAN. After the test solutions (SB) were removed from the exposed layer with a low dielectric by annealing at 150°C for 120 minutes, the thickness is further decreased, especially in layers that have been exposed to the test solutions (SB) containing 2 wt.% and 4 wt.% TMAN.

In contrast to the untreated layers with ultra-low dielectric constant almost all exposed layers with ultra-low dielectric constant showed a significant increase in their refractive index, in particular those groups that were exposed to test solutions (SB) containing 2 wt.% and 4 wt.% TMAN. After the test solutions (SB) were removed from the exposed layer with a low dielectric by annealing at 150°C for 120 minutes, the refractive index increased even more, especially in layers that have been exposed to the test solutions (SB) containing 2 wt.% and 4 wt.% TMAN.

These results showed that high concentrations TMAN has led to significant damage of a material with a low dielectric constant due to the high intensity of trawl�of the respective test solutions (SB).

No adverse effects of this kind was not observed when layers with a low dielectric constant were exposed to test solutions (SB) containing <0.5 wt.% TMAN. In these cases, the intensity of the etching was below 1 nm/min.

The experiments were repeated with layers with a low dielectric constant that have been subjected to a fluorine-containing plasma for etching is typically used for selective etching to obtain the conductive grooves and through holes. It turned out that layers with a low dielectric constant is damaged by plasma, even more resistant to the test solutions (SB) containing <0.5 wt.% TMAN than undamaged layer with ultra-low dielectric constants.

The experiments were repeated with samples of copper discs. It turned out that the test solutions (SB) containing <0.5 wt.% TMAN, showed an etching rate lower than 1 nm/min, while the test solutions (SB) containing more than 1 wt.%, 2 wt.% and 4 wt.% TMAN, showed a much higher etching speed.

Similar results were obtained with a hydroxide of tetrapropylammonium, hydroxide of tetrabutylammonium hydroxide and benzyldimethyl ammonium. The reactivity of these Quaternary ammonium hydroxides are lower than TMAN, and decreases in CC�sannom order. This opens up the possibility of fine adjustment of the compositions and their easy adaptation to the special conditions of manufacturing.

Summarizing, these findings indicate that the most suitable composition containing the polar organic solvents (A), selected according to Example 1, and Quaternary ammonium hydroxides, in particular TMAN, in small concentrations, and extraordinary suited and can be advantageously used as compositions for removing resist to get rid of structured photoresists, polymeric barrier anti-reflective layer and the etching sludge during the fabrication stage (back-end of the line, BEOL) process demaskirovanie using copper for the manufacture of IP VLI and VLSI without damaging the materials with ultralow dielectric constant or etching copper surfaces.

Example 3

The use of compositions containing low concentrations of polar organic solvents (A) and TMAN, as compositions for removing resist

For Example 3 was applied 300 mm-high silicon semiconductor wafer, covered, in the following order, a layer thickness of 30 nm made of silicon carbide to prevent the etching, the layer thickness of 386 nm with ultra-low dielectric constant of doped carbon silicon oxide, a layer of rigid m�ski thickness of 39 nm titanium nitride, polymeric barrier anti-reflective layer thickness of 28 nm, containing absorbing far ultraviolet radiation group, and the layer thickness of 60 nm positive resist sensitive to far-UV radiation with a wavelength of 194 nm, on the basis of a methacrylate copolymer containing Adamantine and laktonovye group.

Coated silicon semiconductor wafer is selectively subjected to far-UV radiation with a wavelength of 194 nm using the test mask, possessing different holes with dimensions less than 100 nm, thereby diluting the negative region of the resist exposed to radiation. Then the mask was removed and the irradiated resist layers were processed with an aqueous solution of sodium hydroxide to obtain the desired resist patterns.

The upper surface of the coated silicon wafer was then treated by fluorine plasma for etching, using the patterned resist as a mask, thereby removing polymeric barrier anti-reflective layers, layers of the hard mask nitride of titanium, are not protected by the patterns in the resist layer. At this stage of the process layers with a low dielectric constant were not etched through, and at most, only a relatively small depth of the full thickness of the layers with ultra-low dielectric constants.

Compositions for the removal of the resist were obtained by mixing the ingredients in the required quantities and homogenising the obtained mixture. Components and their amounts shown in Table 3. Quantities are given in percent by weight, based on the total weight of the respective compositions for the removal of the resist.

Table 3
Components of the compositions for removing resist and number
The number of the example(A) the Amount of solvent/%(B) the Number TMAN/%(C) the Amount of water /%(E) the Amount of benzotriazole/%
3.1S1 98.70.060.241
3.2S2 98.70.060.241
3.3S3 98.70.060.241
3.4S4 98.70.0 0.241
3.5S5 98.70.060.241

Compositions for the removal of the resist with 3.1 3.5 Table 3 had a dynamic viscosity at 50°C, measured by rotational viscometry in the range from 2 to 5 MPa·s. They were used for the removal of structured resists, structured barrier anti-reflective layer and the etching sludge treated with coated silicon wafers. To this end, the plate was placed in a beaker and subjected to stirred (100 rpm) compositions for removal of the resist at 50°C for 300 sec. Then the plates were removed from the compositions for removing resist, washed with isopropanol and then with water and dried under a stream of dry nitrogen at 50°C. After cooling to room temperature the structure of the hard mask was tested for the presence of defects using AFM (atomic force microscopy) and SEM (scanning electron microscopy).

In all cases, the thickness of the structured hard mask exactly equal to their original thickness, indicating that the composition for removing the resist is completely removed structured resists, structured barrier enlightening SL�and and pickling sludge without destruction of the layer with a low dielectric constant. Structured hard mask accurately reproduced the structure of the tested masks. No defects, deformities, scars, residuals or re-osadivshih materials were found, which further emphasizes that the composition for removing resist layer showed excellent cleaning ability at the same time with great compatibility.

Example 4

The use of compositions containing polar organic solvents (A) and TMAN in low concentrations, to remove positive and negative photoresists and etching sludge and the compatibility of these compositions with an adhesive material connecting the thin silicon wafer with the substrate.

Compositions 3.1 to 3.5 of Example 3 was used to implement the Example 4.

Samples of silicon wafers covered with a layer of commercially available positive resists or negative resists, having a thickness of 3.5 μm, 7 μm and 5 μm were respectively subjected to the action of the compositions 3.1 to 3.5 at 65°C for 5 minutes in the beakers. They were subsequently rinsed with deionized water for 3 minutes and dried using a nitrogen gun.

Compatibility with the adhesive materials were tested in the same way.

Optical control and IR-spectroscopy with Fourier transform can confirm that the resists were removed completely covered with semiconductor equipment�lateral plates. On the other hand, the adhesive materials were not destroyed by the compositions 3.1 to 3.5.

Remove positive photoresists, negative photoresists and etching sludge samples with structured silicon wafers with tin-conclusions, copper coating and TSV, tested in the same way. With the help of X-SEM to confirm that the compositions 3.1 to 3.5 were able to completely remove photoresists and residues without damaging the delicate structures.

1. A method of manufacturing an electric device containing stage
1) applying an insulating dielectric layer consisting of at least one material with a low or ultra-low dielectric constant on the substrate surface,
2) applying a positive or negative of the resist layer on the surface of the insulating dielectric layer (1),
3) exposure of the resist layer (2) selective exposure to electromagnetic radiation or corpuscular radiation,
4) manifestation selectively subjected to the radiation of the resist layer (3) for the formation of the pattern in the resist layer,
5) dry etching the insulating dielectric layer (1) using the pattern in the resist (4) as a mask for formation of conductive grooves and/or through holes communicating with the surface,
6) selecting at least one polar organic Sol�sideh of (A) from the group consisting of: Diethylenetriamine, N-methylimidazole, 3-amino-1-propanol, 5-amino-1-pentothal and dimethylsulfoxide, manifesting in the presence of from 0.06 to 4 wt. % dissolved hydroxide of Tetramethylammonium (In), mass fraction of which is taken, based on the total weight of the respective test solution, a constant intensity of removal at 50°C for polymeric barrier anti-reflective layer thickness of 30 nm containing chromophoric groups that absorb in the far UV radiation, 7) providing at least one composition for removing resist, nestorgames N-alkylpyridine and hydroxylamine and hydroxylamine derivatives and having a dynamic shear viscosity at 50°C from 1 to 10 MPa·s, measured by rotational viscometry and comprising based on the total weight of the composition,
(A) from 40 to 99.95 wt. % of at least one polar organic solvent selected in accordance with stage (6) the process
(B) from 0.05 to<0.5 wt. percent based on the total weight of the composition, of at least one Quaternary ammonium hydroxide, and
(C) <5 wt. percent based on the total weight of the composition, of water,
8) removal of the pattern in the resist layer and the etching sludge using the wet process using at least one composition for the removal of the resist (7), obtained in accordance with stage (7) of the process, and
9) filling conductive�x grooves (5) and through holes (5) at least one material, having low electric resistance.

2. A method according to claim 1, characterized in that the Quaternary ammonium hydroxide (B) is selected from the group consisting of hydroxides of Tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, benzyltrimethylammonium and (2-hydroxyethyl)ammonium.

3. A method according to claim 2, characterized in that the Quaternary ammonium hydroxide (B) is a hydroxide of Tetramethylammonium.

4. A method according to claim 1, characterized in that the composition for removing resist on stage 7) comprises at least one additional component selected from the group consisting of polar organic solvents (D) than that of the solvent (A), corrosion inhibitors (E), chelating agents (F), fluoride salts (G) and surfactant (N).

5. A method according to claim 4, characterized in that the polar organic solvent (D) vibirut from the group consisting of solvents exhibiting in the presence of from 0.06 to 4 wt. % dissolved hydroxide of Tetramethylammonium (In), mass fraction of which is taken, based on the total weight of the respective test solution, the intensity of removal at 50°C for polymeric barrier anti-reflective layer thickness of 30 nm containing chromophoric groups that absorb in the far UV radiation, which increases with increasing the concentration of the hydroxide tetramethyl�onium ().

6. A method according to claim 5, characterized in that the polar solvent (D) is selected from the group consisting of ethanolamine, N-methylethanolamine, N-acylethanolamine, isopropanolamine, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethoxy)ethanol, diethylene glycol, the monoethyl ether of diethylene glycol monobutyl ether, N-(2-hydroxyethyl)piperidine, 1,3-dimethyl-3,4,5,6-tetrahydro-2-(1H)-pyrimidinone and N-(3-aminopropyl)-imidazole.

7. A method according to claim 4, characterized in that the corrosion inhibitor (E) is selected from the group consisting of corrosion inhibitors of copper.

8. A method according to claim 1, characterized in that the layer of hard mask (10) is placed between the resist layer (2) and an insulating dielectric layer (1), and said layer of hard mask (10) is selectively etched using the pattern in the resist layer (4) as a mask in the process (5) process.

9. A method according to claim 1, characterized in that the barrier anti-reflective layer (11) disposed between the resist layer (2) and an insulating dielectric layer (1), and the specified barrier anti-reflective layer (11) is selectively etched using the pattern in the resist layer (4) as a mask in the process (5) process.

10. A method according to claim 9, characterized in that the barrier anti-reflective layer (11) is placed between the layer of hard mask (10) and a resist layer (2), and the specified barrier anti-reflective layer (11) and a layer of hard mask (10) selection� bullied in the process (5) process.

11. A method according to claim 1 or 8, characterized in that the selectively etched barrier anti-reflective layer (11) is removed in the process (8) process.

12. A method according to claim 1, characterized in that copper is used as material (9) having a low electric resistance.

13. A method according to claim 1, characterized in that the manufactured electrical devices are semiconductor integrated circuits, liquid crystal display panels, organic electroluminescent display panels, printed circuit boards, micromachines, DNA chips and microsofty.

14. The use of liquid compositions for the removal of the resist to remove the negative and positive photoresists and etching sludge in the manufacture of 3D stacked integrated circuits and 3D packaging at the level of the plates that contain the adhesive material, by shaping of relief through-connections through the silicon (TSV) and/or by deposition, and by forming the bar of the findings, with the specified liquid composition is free of N-alkylpyridine and hydroxylamine and hydroxylamine derivatives, has a dynamic shear viscosity at 50°C from 1 to 10 MPa•s, measured by rotational viscometry, and contains, based on the total weight of the composition,
(A) from 40 to 99.95 wt. percent based on the total weight of the composition, at least one�Yarnykh organic solvent, selected from the group consisting of: Diethylenetriamine, N-methylimidazole, 3-amino-1-propanol, 5-amino-1-pentothal and dimethylsulfoxide, and exhibiting in the presence of from 0.06 to 4 wt. % dissolved hydroxide of Tetramethylammonium (In), mass fraction of which is taken, based on the total weight of the respective test solution (AB), a constant intensity of removal at 50°C for polymeric barrier anti-reflective layer thickness of 30 nm containing chromophoric groups that absorb in the far UV radiation
(B) from 0.05 to <0.5 wt. percent based on the total weight of the composition, of at least one Quaternary ammonium hydroxide, and
(C) <5 wt. percent based on the total weight of the composition, of water.



 

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20 ex

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FIELD: physics.

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FIELD: electricity.

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14 cl, 3 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to composition for photoresist removal after ionic implantation, which contains: (a) amine, (b) organic solvent A, and (c) co-solvent, where content of water in composition constitutes less than 0.5 wt % of composition; amine represents quaternary ammonium hydroxide and is present in quantity from 1 to 4 wt % of composition; organic solvent A is selected from the group, consisting of dimethylsulphoxide (DMSO), dimethylsulphone (DMSO2), 1-methyl-2-pyrrolidinone (NMP), γ-butirolactone (BLO)(GBL), ethylmethylketone, 2-pentanone, 3-pentanone, 2-hexanone and isobutylmethylketone, 1-propanol, 2-propanol, butyl alcohol, pentanol, 1-hexanol, 1-heptanol, 1-octanol, ethyldiglycol (EDG), butyldiglycol (BDG), benzyl alcohol, benzaldehyde, N,N-dimethylethanolamine, di-n-propylamine, tri-n-propylamine, isobutylamine, sec-butylamine, cyclohexylamine, methylalanine, o-toluidine, m-toluidine, o-chloroaniline, m-chloroaniline, octylamine, N,N,-diethylhydroxylamine, N,N,-dimethylformamide and their combination; co-solvent is selected from the group, consisting of isopropyl alcohols, isobutylalcohols, sec-butyl alcohols, tert-pentyl alcohols, ethyleneglycol (EG), propyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanediol, 1-amino-2-propanol, 2-methylamino-ethanol (NMEA), N-ethyldiisopropylamine and their combination; and quantity of organic solvent A and co-solvent constitutes 84, 90-99 wt %. Claimed invention also relates to method for photoresist removal after ionic implantation.

EFFECT: obtaining water-free composition for photoresist removal after ionic implantation.

11 cl, 2 dwg, 5 tbl, 5 ex

FIELD: technology for making images of extremely high resolution.

SUBSTANCE: device has source for producing electromagnetic radiation in range of wave length 100 nm and below, space modulator, having multiple pixels, electronic system for processing and transferring data, receiving digital description of drawing, subject to being drawn, separating from it a series of partial drawings, forming said partial drawings as modulator signals and sending said signals into modulator, and precision mechanical system for moving said block and/or projection circuit relatively one another. Device also has electronic control system coordinating movement of block, sending signals into modulator and intensiveness of radiation, so that said drawing was sewn together of partial images, formed by series of partial drawings.

EFFECT: device using electromagnetic radiation source in waves range 100 nm and below.

8 cl, 7 dwg

FIELD: cryoelectronics.

SUBSTANCE: proposed method used in manufacturing thick-film high-temperature superconductor circuit includes low-temperature firing of substrate followed by laser milling of grooves for paste and scanning with laser beam of area , where Sm is laser beam area in groove milling; Tev and Tmlt are material evaporation and substrate melting temperatures, respectively. Proposed method is characterized in maximal firing temperature reduced from 1600-1700 to 100-1100°C and, consequently, in reduced time, as well as in using laser packing of surface instead of high-temperature firing stage.

EFFECT: enhanced productivity, reduced power requirement.

1 cl, 2 dwg

FIELD: thin-film technology; hybrid integrated-circuit manufacture.

SUBSTANCE: proposed method for manufacturing microwave hybrid integrated circuit characterized in high-quality insulation of its circuit components, reduced probability of failure due to probable shorts at intersection points of image components and pendant wiring conductors and premature degradation of physical and chemical properties of current-carrying tracks, enhanced intervals between layout components at reduced gaps between its components includes creation of image of passive and switching components on substrate surface which are then covered with polyamide insulating layer by way of centrifuging interrupted to provide for certain time interval prior to reducing fluidity of polyamide varnish as it starts drying; during this time interval integrated circuit is held under condition of mentioned varnish spreading throughout entire surface of layout image of mentioned components including their side surface; clearances between component are filled up, and polyamide varnish is dried out. Then, while preparing integrated circuit to wiring of pendant components and conductors, double-layer shielding and insulating coating is formed on image surface at points of intersection of these components in the form of specially saved insulating layer combining functions of additional insulating layer preventing premature degradation of physical and chemical properties of image components and enhancing their insulation and contrast layer designed to improve optical-vision quality control by way of mentioned polyamide varnish photolithography using positive photoresist, as well as auxiliary positive photoresist layer on polyamide varnish insulating layer applied to surface of image components; both layers of this insulating coating are jointly subjected to thermal strengthening; mentioned layers are applied while forming double-layer shielding and insulating coating at the same time saving total thickness complying with main electrophysical parameters of integrated circuit affording admissible microwave mode of its operation.

EFFECT: facilitated manufacture, enlarged functional capabilities.

2 cl, 1 dwg

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