Depositing doped zno films on polymer substrates by chemical vapour deposition under uv action
SUBSTANCE: invention relates to a method of forming a transparent doped layer containing zinc oxide on a polymer substrate for optoelectronic devices and a transparent doped layer. The method includes contacting a polymer substrate with at least one precursor containing a dopant and zinc, and exposing to ultraviolet light during chemical vapour deposition to decompose at least one precursor and deposit a layer on the polymer substrate. The polymer substrate is selected from a group consisting of fluoropolymer resins, polyesters, polyacrylates, polyamides, polyimides and polycarbonates. The contacting step is carried out at pressure approximately equal to atmospheric pressure.
EFFECT: providing a chemical vapour deposition method for depositing doped zinc oxide films on polymer substrates for use in optoelectronics.
12 cl, 1 tbl, 8 dwg, 2 ex
The invention relates to a method of chemical deposition from the gas phase for the deposition of doped films of zinc oxide on polymer substrates.
BACKGROUND of the INVENTION
Transparent conductive oxides (TCO) are oxides of the metals used in optoelectronic devices such as flat panel displays and devices for converting light energy into electricity. In particular, TCO are a class of materials that are optically transparent and electrically conductive. Application are tin-doped indium oxide (ITO), one of the types of TCO, was widely used as a TCO layer in many applications, such as thin film transistors (TFT), liquid crystal displays (LCD), plasma display panels (PDPs), organic light-emitting diodes (OLED), solar cells, electroluminescent devices, and radio frequency ID (RFID). Although the chemical stability of ITO is quite sufficient for many applications, the ITO film can be unstable in a reducing conditions and can collapse under the influence of high electric fields, leading to the formation of the active species of India and oxygen that can diffuse into the organic layers. In addition, due to the lack of India and rapidly growing markets, large-scale to produce flat panel displays and photoelectric the ski new generation of devices is expensive and difficult. So for future technologies desirable new TCO materials to replace or enhance existing ITO materials. In particular, new materials, preferably, should have a low price and can have the same or better electrical and optical properties compared to ITO.
TCO films are often applied on the glass substrate. However, there is an urgent need to replace the glass substrates cheaper, lighter, and/or flexible substrates. Properties of TCO films often depend on the substrate temperature during deposition. Certain substrates, such as polymeric substrate, however, may be heat-sensitive and may experience spatial and structural instability when exposed to higher temperatures (such as 300-500°C). But even at lower temperatures (such as 100-150°C) spatial sustainability of many polymers can be low. In addition, thermal effects can lead to increased tension of the film and damage due to delamination from the substrate. So for TCO films is difficult to achieve the desired electrical and optical properties even at low temperatures. Several technologies, such as pulsed laser deposition (PLD) and RF magnetron sputtering is used for deposition of TCO films on polymer substrates at room temperature is round. These techniques, however, also have additional restrictions, such as lower optoelectronic properties, low speed application, high vacuum, the small size of the application, and so on
BRIEF description of the INVENTION
Aspects of the present invention include methods of obtaining high-quality TCO films on polymer substrates at low temperature method and products available from them.
According to the implementation of the present invention a method of forming a layer on a polymer substrate includes contact polymeric substrate with at least one precursor and the action of ultraviolet light to decompose at least one precursor and the coating layer on the polymer substrate.
According to the implementation of the present invention a method of forming a doped layer containing zinc oxide on polymer substrates, includes contact polymeric substrate with at least one precursor containing zinc and alloying additive, and the action of ultraviolet light to decompose at least one precursor for the deposition of a layer containing doped zinc oxide, on a polymer substrate.
According to another implementation of the present invention doped layer comprising zinc oxide deposited on a polymer substrate, is produced by introducing at least one is of recursor, containing zinc alloying elements and the source of oxygen in the mixing chamber, which passes through the UV chamber, after which the layer containing doped zinc oxide, is applied to a polymeric substrate.
According to another implementation of the present invention a method of forming a layer on a polymer substrate includes contact polymeric substrate with at least one precursor, and the action of ultraviolet light to decompose at least one precursor and the coating layer on the polymer substrate at a temperature less than about 200°C.
BRIEF DESCRIPTION of DRAWINGS
Fig.1 is an optical transmittance of the PVDF substrate and ZnO on PVDF.
Fig.2 is an x-ray diffraction patterns of ZnO films on glass or PVDF substrates.
Fig.3 is a UV spectrum of Hg metal halide high pressure.
Fig.4 is a graph of resistivity of Al-doped ZnO films depending on time after application.
Fig.5 is a theta-theta x-ray diffraction, is investigated in the bulk.
Fig.6 is the x-ray diffraction incidence (1 degree), studied on the top surface of the samples.
Fig.7 is a profile depth of sample 170-2.
Fig.8 is a profile depth of sample 171-1.
DETAILED description of the INVENTION
Aspects of the present invention include a method is the formation of a layer on a polymer substrate and products obtained from it. In particular, the implementation of the present invention provide a method for the deposition of doped films of zinc oxide on polymer substrates.
As used herein, unless otherwise indicated, the values of composite parts or components, expressed in mass percent or weight. % of each ingredient. All values listed in this document include limits and including the endpoints.
Polymeric substrates suitable for use in the present invention include any of the substrates that can be put on a coat, for example, in the method of chemical deposition from the gas phase. Especially suitable transparent polymeric substrate. For example, substrates can be used materials having a glass transition point (Tg) at a temperature less than 400°C, the coating is applied at a temperature of the substrate is less than 400°C (e.g., between approximately 80°C and 400°C). In a preferred embodiment, the polymeric substrate is transparent (for example, transmittance of more than 80%).
Illustrative examples of suitable substrate materials include, but without limitation, polymeric substrate, such as polyacrylates (e.g., polymethylmethacrylate (pMMA)), polyesters (e.g. polyethylene terephthalate (PET), polyethylenterephthalat (PEN), polyarylate Piketon (PEEK) and polyetherketoneketone (PEKK)), polyamides, polyimides, polycarbonates and the like. In the embodiment of the present invention a polymer substrate selected from the group consisting of fluoropolymer resins, polyesters, polyacrylates, polyamides, polyimides and polycarbonates. In another embodiment, the polymer substrate selected from the group consisting of polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), polyethylenterephtalate (PEN) and polymethylmethacrylate (PMMA). In a preferred embodiment, the polymeric substrate is a poly (vinylidene fluoride) (PVDF). In another preferred embodiment, the polymeric substrate is a polyethylene terephthalate (PET) or polietilentereftalata (PEN). In another preferred embodiment, the polymeric substrate is polyetherketoneketone (PEKK) or polymethylmethacrylate (pMMA).
The polymer can also be made to other components. For example, fillers, stabilizers, dyes, etc. can be added and included in the polymer or applied to the surface of the polymer, based on the required properties.
The substrate may be in any suitable form. For example, the polymer substrate can be a sheet, film, composite, or the like. In a preferred embodiment, the polymeric substrate is a film in the form of a roll (for example, for roll technology).The polymeric substrate can be any suitable thickness, based on the application. For example, the polymer substrate may be less than approximately 15 mils (thousandths of an inch) in thickness.
According to a variant implementation of the present invention a method of forming a layer on a polymer substrate includes contact polymeric substrate with at least one precursor, at the same time applying ultraviolet light to decompose at least one precursor, and applying a layer of TCO on a polymer substrate.
Ultraviolet (UV) light is used for decomposition of at least one precursor. Ultraviolet light is an electromagnetic radiation with a wavelength shorter than the wavelength of visible light, but longer than x-rays, for example, in the range from 10 nm to 400 nm with a photon energy of 3 eV to 124 eV. In a preferred embodiment, the wavelength of the UV light is in the range of 180-310 nm, preferably 200-220 nm. In certain embodiments of the implementation of the light may be monochromatic. UV light can photochemically decomposing and/or activating the precursors. In addition, UV light may precipitate or contribute to the TCO deposition on polymer substrates.
In one embodiment, the UV light may be applied during the method of chemical deposition from the gas phase. Chemical deposition from the gas phase (CVD) is a chemical method, use the method to obtain high-purity, high-performance solid materials and is often used in the semiconductor industry to produce thin films. In a typical CVD method, the substrate is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface with the formation of the desired coating or film. The coating or film may contain one or more types of metal atoms, which may be in the form of metals, metal oxides, metal nitrides, or etc., after the reaction and/or decomposition of the precursors. Any forming volatile by-products are commonly removed by gas flow through the reaction chamber.
Chemical deposition from the gas phase, however, may be limited, especially in respect of the used substrates. For example, the temperature of application for most methods of chemical deposition from the gas phase at atmospheric pressure (APCVD) is 400-700°C, which is outside of the temperature of thermal stability for most polymers. It was found that at lower temperatures (for example, up to approximately 150°C) for aligning polymer substrates without the use of chemical deposition from the gas phase, under the influence of UV were deposited film of zinc oxide with low conductivity. Potential contentious issue at low temperature Nan the attachment may be that energy, announced at lower temperatures may not be sufficient for decomposition and activation of the precursor. Therefore, it was determined that additional energy source, for example, to activate precursors and deposition of TCO films with good optoelektronische properties. Accordingly, embodiments of the present invention is used for UV photochemical decomposition, and/or activation of the precursor and/or the successful application of high-quality TCO films on polymer substrates.
The polymer substrate is in contact with at least one precursor. The precursor can include one or more types of precursors. The precursor(s) may be any suitable precursor known to the person skilled in the art. The precursor may be introduced into the system in any suitable form. In the implementation of the precursor(s) are preferably introduced into the gas phase (i.e., in the form of vapor). For example, preferred are suitable gaseous precursors for use in the method of chemical deposition from the gas phase. Preferably, the precursors for chemical vapor deposition (CVD) were volatile, and easy to handle. Desirable precursors exhibit sufficient thermal stability to prevent premature destruction or contamination of the substrate and at the same the time facilitate easy handling. In a preferred embodiment, the precursor must be deposited at a relatively low temperature to preserve the characteristics of the substrate or underlying layer formed previously. In addition, preferably, the precursors for use in the methods of shaneshane had minimal or no detrimental effect on coherent coats, when used in the presence of other precursors.
In the embodiment of the present invention, at least one precursor contains zinc. Can be used any suitable zinc-containing compounds. The connection is preferably zinc is introduced in gaseous form. Zinc can be entered, for example, in the form of oxide, carbonate, nitrate, phosphate, sulfide, halogenated zinc compounds, zinc compounds containing organic substituents and/or ligands, and so on
For example, the zinc-containing compound can correspond to the General formula:
R1R2Zn or R1R2Zn·[L]n,
where R1and R2the same or different and selected from alkyl groups or aryl groups, L is a ligand, n is equal to 1, if L is a polydentate ligand (e.g., bidentate or tridentate ligand), and n equals 2, if L is a monodentate ligand. Suitable ligands include, for example, e the Ira, amines, amides, esters, ketones and the like. Polydentate ligand may contain more than one type of functional groups that can coordinate with the zinc atom.
Other suitable zinc-containing compounds include, but without limitation, the compounds of the General formula:
where R1-8may be the same or different alkyl or aryl groups such as methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, phenyl or substituted phenyl, and may include one or more fluorine substituents; L is based on the oxygen neutral ligand, such as ether, ketone or ester, and z=0-2. R5and R6can be H or alkyl or aryl groups, n can be 0 or 1, m can be 1 to 6 when n equals 0, and m can be 0-6, if n equals 1.
Other suitable zinc compounds may include dialkylzinc alkyl glycol ethers of the General formula:
where R9is a short chain, saturated organic group having 1 to 4 carbon atoms (in this case two groups of R9may be the same or different), and R10is corotation what I saturated organic group having 1 to 4 carbon atoms. Preferably R9is a methyl or ethyl group, R10is a methyl group, and is referred to as diethylzinc (DEZ) diglyme, having the formula:
Some examples of suitable zinc compounds include, for example, adducts diethyl - and dimethylzinc, such as diethylzinc·TEEDA (TEEDA - N,N,N',N'-tetraethylethylenediamine), diethylzinc·TMEDA (TMEDA - N,N,N',N'-tetramethylethylenediamine), diethylzinc·TMPDA (TMPDA - N,N,N',N'-tetramethyl-1,3-propandiamine), dimethylzinc·TEEDA, dimethylzinc·TMEDA and dimethylzinc·TMPDA.
Other suitable zinc-containing compounds include, for example, carboxylates of zinc (such as zinc acetate, zinc propionate), diketonates zinc (for example, zinc acetylacetonate, hexafluoroacetylacetonate zinc), valkirye zinc compounds (for example, diethylzinc, dimethylzinc), zinc chloride and the like.
If zinc is included as a precursor, the method of forming the doped layer comprising zinc oxide on polymer substrates, includes contact polymeric substrate with at least one precursor containing zinc and alloying additive, and the action of ultraviolet light to decompose at least one precursor for the deposition of a layer containing doped oxide C is NSV, on a polymeric substrate. According to a preferred variant implementation of a transparent conductive oxide layer is a layer of doped zinc oxide. The layer of zinc oxide, however, may be alloyed or not.
In the embodiment of the present invention, at least one precursor contains alloying additive. Can be used any suitable alloying additives, known to specialists in this field. For example, can be used alloying additives commonly used in the method of chemical deposition from the gas phase. The alloying additive is preferably introduced into the gas phase. In a preferred embodiment, the alloying additive represents at least one metal selected from the group consisting of Al, Ga, In, Tl and B. More preferably, the alloying additive is a Ga.
For example, the precursor composition can include one or more precursors containing metals 13 groups, including the precursors of the General formula:
where M is B, Al, Ga, In or Tl, R9is alkyl or aryl, or halide, or alkoxide group, R10-12may be the same or different and represent H, alkyl or aryl group (including a cyclic andpartially and fully fluorinated derivatives), n=0-3, and L is a neutral ligand capable of coordinating with metal. Preferred kalisoderjasimi precursor is dimethyldichlorosilane (usually referred Me2Ga(hfac)). Other suitable kalisoderjasimi precursors can include datingare (hexafluoroacetylacetonate), trimethylgal lium, trimethylgal lium (tetrahydrofuran), triethylgallium (tetrahydrofuran), dimethylallyl (2,2,6,6-tetramethyl-3,5-heptanedionato), dimethylallyl (acetylacetonate), Tris(acetylacetonate)gallium, Tris(1,1,1-cryptorchidectomy)gallium, Tris(2,2,6,6-tetramethyl-3,5-heptanedionato)gallium and triethylgallium. Other kalisoderjasimi compounds may also be suitable for use as precursors in the present invention.
Suitable aluminium-containing precursors may include R1(3-n)AlR2nand R13Al(L), where R1is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or octyl, R2is a halide or a substituted or unsubstituted derivative of acetylacetonate, including partially and fully fluorinated derivative, n is 0 to 3, and L is a neutral ligand capable of coordination with aluminum. Preferred aluminium-containing precursors may include diethylaminoethylamine (Et2Al(acac)), diethylaluminium, IER is illumini(hexafluoroacetylacetonate), diethylaluminium(1,1,1-cryptorchidectomy), diethylamine(2,2,6,6-tetramethyl-3,5-heptanedionato), triethylamine, Tris(n-butyl)aluminum and triethylaluminium(tetrahydrofuran). Other aluminium-containing compounds may be suitable for use as precursors in the present invention.
Suitable boron, indium and callistitae compounds that can be used as an alloying agent precursors include DIBORANE, as well as connections similar to aluminum - and kalisoderjasimi compounds mentioned above (for example, compounds where the atom B, In or Tl substituted by Al or Ga in any of the above-mentioned aluminum - or geliysoderzhaschih precursors).
The amount of alloying (for example, species of Al, B, Tl, In, Ga, such as oxides) in the final coating alloyed oxide can be controlled optionally by controlling the composition of the vapor precursor, for example, the relative amounts of precursors. In one embodiment, the oxide coating contains from about 0.1% to about 5% or from about 0.5% to about 3% by weight of the alloying oxide.
Additional components can be added to the precursor before or simultaneously with the contact vapor precursor with the substrate.
Such additional components or precursors may include, for example, oxygen is tsagarada connection in particular, compounds that do not contain metal, such as esters, ketones, alcohols, hydrogen peroxide, oxygen (O2) or water. One or more fluorine-containing compounds (for example, fluorinated alkanes, fluorinated alkenes, fluorinated alcohols, fluorinated alcohols, fluorinated carboxylic acids, fluorinated esters, fluorinated amines, HF or other compounds containing F but not metal) may also be used as an additional component. Pair precursor can be mixed with an inert carrier gas, such as nitrogen, helium, argon or the like.
In the embodiment of the present invention a method of forming a layer on a polymer substrate includes contact polymeric substrate with at least one precursor and the action of ultraviolet light to decompose at least one precursor and the coating layer on the polymer substrate. In a preferred embodiment, the step of contact and/or phase of the UV light may leak under low temperature conditions. In particular, low-temperature conditions can occur when less than approximately 400°C. In the variant example of implementation, the step of exposure to UV occurs at less than about 200°C, for example 100-200°C, preferably approximately 160-200°C. In a preferred embodiment, implemented the surveillance stage UV proceeds at approximately 160-200°C. For example, if you are using the method of chemical deposition from the gas phase, it is assumed that the low-temperature conditions can occur at any time during the method, preferably the entire way, to minimize adverse effects on the polymer substrate. During contact and exposure can be applied to any suitable conditions. For example, the stage of contact, and/or the phase of the exposure can be performed at approximately atmospheric pressure. Accordingly, in a preferred embodiment, the method is a method of chemical deposition from the gas phase at atmospheric pressure (APCVD). Can also be used any other suitable conditions or techniques such as chemical deposition from the gas phase at low pressure (LPCVD), plasma-chemical deposition from the gas phase (PECVD), physical deposition from the gas phase, and so on
It is recognized that the stages of contact and exposure can take place in any suitable manner. For example, in the chemical deposition from the gas phase, the gas stream containing at least one precursor is introduced into the camera application. The gas can move in the direction of flow through the reactor. Precursor components or products of the reagent can diffuse across the direction of flow and contact with the surface of the substrate as as the precursors are activated and decompose, they are applied to the substrate and form a film or layer. Accordingly, it may be contact between the precursor and/or activated/decomposed product and the polymer substrate. Accordingly, the method of forming a layer on the polymeric substrate may include depositing at least one precursor of the polymer substrate and the ultraviolet light to decompose at least one precursor for the deposition of a layer on a polymer substrate. In a preferred embodiment, the method is a method of chemical deposition from the gas phase.
When using the method of chemical deposition from the gas phase precursors containing zinc alloying additive and the source of oxygen in the gas phase is injected into the mixing chamber, and then passed through the UV chamber, then put on a polymeric substrate layer containing doped zinc oxide. The method of chemical deposition from the gas phase can also be done during roll technology (or drum) where the application is done on a polymer substrate from a roll, for example, in a continuous way.
The methods disclosed in this document, produce the layer, optionally doped layer deposited on a polymeric substrate. Making unactivated precursor (in part is but the unfolded state) in the layer is minimized or eliminated. The method of application can be carried out with the formation of a TCO layer or several layers of TCO. The layers may be the same or different layers of TCO. The TCO film may be of any suitable thickness. For example, the film may be in the range of about 1000-8000 Å. In a separate embodiment, the method of application can produce a film of zinc oxide doped with gallium.
The TCO layer preferably has high quality, with excellent electrical and optical properties. Preferably, the properties of the TCO layer, especially of the doped zinc oxide, were at least comparable, if not better, than doped tin indium oxide (ITO). For example, ITO may be uniformly distributed resistivity, for example, in the range from about 1×10-4Ohm·cm to 3×10-4Ohm·see In an exemplary embodiment, a transparent conductive oxide layer has a resistivity less than about 1×10-3Ohm·cm thick Layer should also exhibit good optical properties. In particular, TCO can provide the transmission of visible light greater than 80%, more preferably more than 90%.
Using embodiments of the present invention, it is possible to obtain a coating which is electrically conductive, transparent in visible light, reflecting infraclass the e radiation and/or absorbing ultraviolet light. For example, coated with zinc oxide transparent material substrate having a high transmittance of visible light, low emission properties and/or properties of the solar energy, as well as high conductivity/low surface resistance can be obtained by implementing the present invention.
In addition, it is assumed that the TCO layer exhibits good wear resistance, for example, through the manifestation of good adhesion to the substrate (for example, the coating will not flake off over time). The TCO layer is stable, undergoing the method of annealing (for example, atoms of the alloying substances can diffuse into substitutional positions in the crystal lattice, causing changes in electrical properties).
Possible applications of TCO films made in accordance with the present invention include, but without limitation, a thin-film photovoltaic (PV) and organic photovoltaic (OPV) devices, flat panel displays, liquid crystal display devices, solar cells, electrochromic absorbers and reflectors, energy-saving heat-reflecting mirrors, anti-static coating (e.g., masks), solid state lighting (LED and OLED), induction heating, gas sensors, optical transparent conductive film, transparent heating elements (EmOC is emer, for various protivobolevye equipment, such as refrigerated cabinets), touch panels and thin-film transistors (TFT), and low-emission layers and/or layers of control of solar energy and/or heat-reflecting film in applications in the architectural and transportation boxes and such. In a preferred embodiment, the TCO film may be used as thin-film PV and OLED (more specifically, lighting OLED).
Al or Ga-doped film of zinc oxide (ZnO) were deposited using the method of UV-chemical deposition in the vapour phase (UV-CVD). The method of application differs from conventional chemical deposition from the gas phase at atmospheric pressure so that there is a source of UV light to activate the precursors and promote the deposition at a low temperature substrate. Zinc is a precursor used in the method was complex dimethylzinc and methyl-THF. Al and Ga doping substances - acetylacetonate diethylaluminum (Et2Al(acac)) and acetylacetonate of dimethylallyl (Me2Ga(acac)), respectively. The oxidant used in the way that was either water, or a mixture of water and alcohol. Nitrogen was used as carrier gas to transfer as vapor precursor and vapor oxidizer to CVD mixing chamber prior to application to the substrate. Zn and alloying materials were stored in steel bubblers, and the carrier gas is nitrogen flowed through the bubblers and endured a couple of precursors into the mixing chamber. The experimental parameters are listed in table 1. Has been tested many sources of UV light to activate the application: mercury lamp, medium pressure Hanovia, amalgam lamp low pressure Heraeus and metal halide lamp high pressure Heraeus. And a mercury medium pressure lamp, and metal halide lamp high pressure generate a broad spectrum of radiation, covering from UVC (~220 nm) to the infrared, whereas amalgam lamp low pressure generates UV radiation at two wavelengths of 185 and 254 nm. Energy flows at 185 and 254 nm are 9 and 30 W, respectively.
|Zn||Al||Water||The carrier gas|
|The pace. covered head (°C)||The pace. substrate (°C)|
|Flow rate (ml/min)||The pace. baths|
|The pace. line (C)||Flow rate (ml/min)||The pace. bath (°C)||The pace. line (C)||The flow rate|
|The rate of infusion (ml/h)||The pace. line (C)|
|100||66||70||300||66||70||6||15||160||10||160||EXT.T. - 200|
EXAMPLE 1: a Mercury lamp, medium pressure Hanovia
Doped ZnO film was applied using UV-CVD using a photochemical reaction vessel. As the source of UV light used mercury lamp, medium pressure Hanovia. PVDF (PVDF) film was wrapped around the cooling of the quartz sleeves as substrates and precursors and oxidants was fed into the reaction vessel carrier gas nitrogen. The application time was approximately 1-2 minutes. The film thickness of approximately 160 nm. Received good coverage with a uniform film thickness and good adhesion to PVDF substrate, but the conductivity was heterogeneous. Al-alloyed ZnO film was conductive in some areas, up to 1×10-3Ohm·see Fig.1 shows that p is a child was highly transparent in the visible light with > 90% transmission.
Fig.2 shows x-ray diffraction (XRD) ZnO on glass, ZnO on PVDF and separately PVDF. Diffraction patterns show that ZnO can be caused by UV-CVD on various substrates, in particular on a polymeric substrate, such as PVDF. The preferred orientation of the crystals depends on the used substrates, that is, (002) dominated on the glass substrate, whereas the (101) prevails on PVDF.
EXAMPLE 2: Hg metal halide lamp high pressure
Hg metal halide lamp high pressure produced by Heraeus, used as a source of UV light in the low-temperature deposition of conductive ZnO films on polymer and glass substrates. Fig.3 shows the lamp spectrum, and the total capacity of this lamp is 400 watts.
Using Hg metal halide lamp high pressure, Al-doped ZnO film was applied on glass, polyetherketoneketone and KAPTON®(registered trademark of E. I. DuPpont de Nemours and Co.) when the temperature of the substrate in the range from room temperature to 200°C. films of ZnO were elektroprovodyashchimi, when the temperature of the substrate was equal to or below 130°C, whereas the films were conductive, when the temperature of the substrate was equal to or exceeded 160°C. This shows that the method of application is activated by a combination of UV and heat. The most conductive Al-Egorovna films of ZnO have surface resistance and specific resistance of about 60 Ohms/square and approximately 4,0×10 -3Ohm·cm, respectively. Resistance conductive films of ZnO in time is very important for maintaining performance and stability of devices such as organic light-emitting diodes, photoelectric and flexible displays. Fig.4 shows the resistivity depending on the time of the content of ZnO films at ambient conditions after application. The film was applied at different temperatures of the substrate. Sample 171-6 inflicted on the KAPTON film®at 180°C, while the other was applied to a glass substrate. Samples 171-1 and 171-5 was applied at 160°C. the ZnO Film deposited at relatively higher temperatures (180 and 200°C), keep the conductivity after approximately 1 month, whereas films deposited at 160°C, gradually over time, partly lose their conductivity.
Fig.5 and 6 show x-ray diffraction patterns of ZnO films in the bulk and at the surface respectively. Both figures show that the films are films of ZnO with characteristic diffraction peaks of ZnO. In the bulk of the c axis of the unit cell of ZnO (002) almost perpendicular to the sample plane for sample 171-1, whereas it is practically in the plane of the sample for sample 170-2. Near the upper surface of the sample visible to the important crystallographic differences between the two samples. Sample 171-1 shows a more random orientation near the poverhnosti, than in volume. Sample 170-2 a stable preferred orientation near the surface, and the c axis of the unit cell of ZnO (002) remains within the plane of the sample compared to the sample 171-1. Axis a (100) oriented along the normal of the sample.
On the surface of a thin film 170-2 there is a thin layer composed of C, Al and O. Then he goes into a thin layer O, Zn, Al and C. the Next layer, the most fat in a thin film, is Zn, O, some C and some amount of Al. Sample 170-2 has a concentration gradient of Al with a surface rich in Al. Fig.7 is a profile depth of sample 170-2. Fig.8 is a profile depth of sample 171-1. Sample 170-2 has good conductivity, and stores the conductivity at ambient conditions. Sample 171-1 has a more traditional-looking profile of concentration, as seen in Fig.4, and shows a very stable profiles of concentrations for Zn, O, and Al. However, the sample 171-1 has a lower conductivity than the sample 170-2.
And the sample 170-2, and the sample 171-1 are rich in oxygen doped ZnO film, and [Zn] and [O] are 35-45% and 55-60%, respectively.
Although this text is shown and described the preferred embodiment of the invention, it will be clear that such implementation is provided only as an example. Numerous variati is, changes and replacements will be made by experts in this field, without departing from the essence of the invention. Accordingly, it is understood that the appended claims cover all such variations as fall within the essence and scope of the invention.
1. The method of forming a transparent doped layer containing zinc oxide on polymer substrates for optoelectronic devices, including:
(a) contacting the polymeric substrate with at least one precursor containing alloying additive and zinc; and
(b) the action of ultraviolet light during the process of chemical deposition from the gas phase to decompose at least one precursor and applying a layer on a polymeric substrate,
where the polymer substrate is selected from the group consisting of fluoropolymer resins, polyesters, polyacrylates, polyamides, polyimides and polycarbonates,
and the stage contacting is carried out at approximately atmospheric pressure.
2. The method of forming a transparent doped layer containing zinc oxide on polymer substrates under item 1, where the alloying additive represents at least one metal selected from the group consisting of Al, Ga, In, Tl, and B.
3. The method of forming a transparent doped layer containing zinc oxide on polymer substrates under item 1, where the submitted layer is a transparent conductive oxide layer.
4. The method of forming a transparent doped layer containing zinc oxide on polymer substrates under item 1, where the transparent conductive oxide layer has a resistivity less than about 1×10-3Ohm·see
5. The method of forming a transparent doped layer containing zinc oxide on polymer substrates under item 1, where step (b) occurs at less than about 200°C.
6. The method of forming a transparent doped layer containing zinc oxide on polymer substrates under item 1, where step (b) occurs at about 160-200°C.
7. The method of forming a transparent doped layer containing zinc oxide on polymer substrates under item 1, where at least one precursor is introduced into the gas phase in step (a).
8. The method of forming a transparent doped layer containing zinc oxide on polymer substrates under item 1, where the polymer substrate is selected from the group consisting of polyvinylidene fluoride (PVDF), polyethylene terephthalate (PET), polyethylenterephtalate (PEN) and polymethylmethacrylate (emission spectra obtained for pure).
9. The method of forming a transparent doped layer containing zinc oxide on polymer substrates under item 1, where the UV light activates at least one precursor.
10. How transparent doped layer containing zinc oxide on polymer substrates under item 1, where the UV is light has a wavelength of about 180-310 nm.
11. The method of forming a transparent doped layer containing zinc oxide on polymer substrates under item 1, where the method is a method of chemical deposition from the gas phase.
12. Transparent doped layer comprising zinc oxide deposited on a polymer substrate obtained by the method according to any one of paragraphs.1-11.
SUBSTANCE: method for carrier concentration determination in semiconductors consists in passage of high-frequency current through a transition shifted both in backward and direction directions, receipt of data on carrier concentration at the depletion region depth out of a production of the second harmonic current amplitude and the first harmonic voltage, which is inversely proportional to charge carrier concentration, detection of a surveyed object by scanning at an atomic-force microscope with conducting probe, formation of the barrier contact to the surveyed nano-object by the microscope probe. The device for implementation of the above method comprises 28 elements.
EFFECT: local detection of concentration of free charge carriers in semiconductor micro- and nano-structures.
2 cl, 1 dwg
SUBSTANCE: solution contains indium (III) salt, tartaric acid, thioacetamide, hydroxylamine hydrochloride with the following reagent concentration, mol/l: indium(III) salt - 0.01-0.2; thioacetamide - 0.01-0.5; tartaric acid - 0.005-0.2; hydroxylamine hydrochloride - 0.005-0.15.
EFFECT: invention makes it possible to obtain films of indium sulphide, which are characterised by higher values of thickness with the simultaneous preservation of high quality of the film surface.
1 tbl, 2 ex
FIELD: physics, computer engineering.
SUBSTANCE: invention relates to computer engineering and specifically to digital signal processing. The heterogeneous processor comprises: a universal processor with a port, an input/output unit with a port, a RAM controller with a port, a unit for rapid execution of digital signal processing algorithms with a port, which consists of a memory direct accessing controller, a program memory unit and a computer section control unit, each consisting of a register file unit with ports, connected to the port of the computer section control unit, a local ROM unit and an arithmetic logic unit, consisting of input register units, output register units, multiplier units and adder units, installed in a number which is sufficient to execute B±C×D operations for each circuit, where B, C and D are complex numbers, real and imaginary parts of which are 32-bit floating-point numbers, and the processor is equipped with a buffer memory unit with ports.
EFFECT: low power consumption per unit output and high processor throughput.
FIELD: process engineering.
SUBSTANCE: proposed device can displace the substrate in several axes with the help of manipulator equipped with electromagnetic moving yoke at its end. Note here that said manipulator is arranged at rotary lifting assy. Said electromagnetic guide support is equipped with active moving element. The latter is fitted at stationary passive element with the help of magnetic supports arranged across magnetic supports. The latter retain active moving element at passive element at equilibrium and as-suspended. Sais active element is equipped with rotary lifting assy. The latter comprises external tube secured vertically at active element. Magnetic supports are arranged inside external tube at equal spacings on external tube outer surface for contactless direction of internal tube in vertically between two extreme positions.
EFFECT: transfer of substrates without friction and formation of particles.
21 cl, 14 dwg
SUBSTANCE: method involves evaporating a target of starting material with a pulsed electron beam with energy of not more than 100 keV, pulse duration of 20-300 mcs, energy density of not less than 1 MJ/cm2; a beam of electrons on the path to the target is passed through a system of generating a gas pressure drop, through which pressure of 1-20 Pa is provided in the evaporation chamber in order to cool particles, wherein particles are deposited on cooled substrates made of metal whose melting point is higher than 900°C, and the coefficient of linear thermal expansion is close to that of the deposited layer of aluminium oxide, the thickness of which is controlled in the range of 5-40 mcm by deposition time of 5-20 minutes, and radiation sensitivity is controlled by final heat treatment in the range of 550-900°C for 10-20 minutes.
EFFECT: high accuracy and reliability of detecting doses of short-range charged particles of nuclear radiations, including complex fields using TL or OSL techniques.
SUBSTANCE: masking coating, and namely perfluoropolyether is applied onto a substrate. Then, a copper layer or an aluminium layer with surface resistance of about 90-110 Ohm/m2 is applied by means of a selective vacuum metallisation method; after that, a current-carrying layer of silver-containing paint with silver content in the amount of 70-90% is applied by means of a screen printing method. Surface resistance of the obtained current-carrying coating is measured by means of a four-probe control method. Sections of the substrate are rejected, which do not correspond to the required technical characteristics determined from the condition of allowable spread of surface resistance of not more than 15% in absolute units.
EFFECT: improving producibility; enlarging operating capabilities; reducing production costs; improving measurement accuracy.
2 cl, 1 tbl
SUBSTANCE: invention relates to the field of nanotechnology and can be used for production of atomic-thin single-crystalline films of various multilayer materials. In the method of production of atomic-thin single-crystalline films, comprising the selection of thin single-crystalline fragments of starting layered single crystals, gluing them to the working substrate is carried out using epoxy adhesive, and the consequent removal of layers from thin single-crystalline fragments using, for example, adhesive tape.
EFFECT: simplification of the manufacturing technology of atomic-thin single-crystalline films.
11 cl, 4 dwg
SUBSTANCE: semiconductor or dielectric condensed medium is exposed to an electromagnetic pulse to generate a circularly or elliptically polarised electromagnetic wave, characterised by that circular polarisation frequency of the electrical component of the field is superposed with the electrostriction frequency of a sound standing wave formed on the surface of a cluster of substance, which generates circular current breakdown on the surface of the cluster, which leads to change in properties of the semiconductor and dielectric condensed substances which relax over time after the electromagnetic exposure stops (echo-signal).
EFFECT: controlling variable parameters of a substance.
2 cl, 13 dwg
SUBSTANCE: in the method of assembling microelectronic components, once a position fixing polymer (4), in order to maintain alignment of microelectronic components (2) that are assembled on a substrate (1) using an anisotropic electroconductive film (7), is applied onto the substrate and hardened, the microelectronic components (2) are heated to a predetermined temperature and compressed at a predetermined pressure using a flexible sheet (5) provided on the microelectronic components and then subjected to single-step compressive fixation on the substrate (1).
EFFECT: providing a method of assembling microelectronic components which, when using an anisotropic electroconductive film to assemble a plurality of microelectronic components of different height on a base plate, allows assembling at precise positions on the base plate, thereby preventing position shift which results from compressive fixation.
5 cl, 16 dwg
FIELD: electrical engineering.
SUBSTANCE: invention is related to the method for manufacturing of wafer holder for electrostatic wafer chuck with acceptable efficiency, free from unsatisfactory removal of semiconductor wafer which is a substrate and is to be treated from the first moment of electrostatic chuck delivery for new usage. The method of electrostatic chuck manufacturing is aimed to coat surface of the holder body having electrodes. It includes stages of sintered body receipt by raw power formation by pressing into a mould and its further sintering, formation, polishing of the sintered body surface, which will contact with substrate; it should be treated up to certain degree of roughness and smoothness; and then performance of spot blasting in order to remove only separable particles which appear in result of the above polishing.
EFFECT: wafer improvement.
2 cl, 2 dwg
SUBSTANCE: group of inventions relates to a polimerisation-able photochromic isocyanate composition, containing a photochromic compound, to a photochromic mesh optical material and to a method of its obtaining. The polimerisation-able photochromic isocyanate composition includes. wt.p.: an organic photochromic compound 1-15; a polymerisation catalyst 0.01-5, polymerisable compounds 100. The polymerisable compounds contain, wt.p.: diisocyanates and/or oligoisocyanurateisocyanates 60-100, monoisocyanates 0-40. The catalyst is used in an amount of 0.01-5 wt.p. per 100 wt.p. of the polymerisable compounds. Also described is the photochromic mesh optical material - the product, obtained by thermal hardening of the polymerisation-able composition, described above, at least, on one surface of a sheet of a transparent substrate, made of polymethylmethacrylate, polycarbonate, polyethyleneterephthalate, cellulose derivatives, polyvinyl alcohol, polyvinylchloride, polyvinylidenchloride, polyethers, polyurethanes. Also described is a method of obtaining the photochromic mesh optical material.
EFFECT: obtaining the polymerisation-able photochromic isocyanate composition with high adhesion ability and product based on it with high optical properties, such as transparency, colourlessness, or colouration, and long-term exploitation.
13 cl, 2 tbl, 25 ex
FIELD: physics, optics.
SUBSTANCE: invention can be used in optical systems of UV, visible and IR optical, optoelectronic and laser devices. A flat-concave lens is made of a plastically deformed piece part, wherein an integral flat surface is perpendicular to an axis of symmetry of the piece part and formed from an apex of the piece part at x0<H, wherein H is the thickness of the piece part. An output surface of the lens has a profile providing measuring the thickness hy=h0×n0/ny, wherein h0 is the lens thickness in the centre, n0 is an ordinary beam refraction index, while ny is an extraordinary beam refraction index at a distance Y from the lens centre. The piece part is made by the plastic deformation of a parallel-sided plate of a crystal Z-section by the central annular bend. The lens surface is formed by removing an excessive layer of the material from the piece part.
EFFECT: producing the leucosapphire lens forming the flat wavefront of extraordinary beams and transparent within 25,000-2,000 cm-1 for a parallel beam of light perpendicular to the input surface.
2 cl, 1 dwg
SUBSTANCE: invention relates to improved method of obtaining workpieces from silver halides and their solid solutions for fibrous infrared lightguides, which includes application on silver halide crystal-core of crystalline shell of crystalline silver halide with refraction index lower than in crystal-core, and thermal processing. Shell on crystal-core is applied by ion-exchange diffusion in ion-exchange source, as the latter taken is finely disperse silver halide powder with coarseness 1-20 mcm, diffusion is carried out at temperature, close to melting temperature of crystal-core in atmosphere of mixture of vapours of halides, included into composition of crystal material and powder, taken in equal ratio under pressure 0.2-0.5 atm.
EFFECT: method makes it possible to reduce optic loss of lightduides, operating in infrared spectrum range.
SUBSTANCE: multilayered coating contains three successive layers with an even thickness: a lower mirror metal radio-reflecting skin-layer of pure aluminium, an intermediate protective thermoregulatory dielectric layer of zirconium dioxide and an upper protective wear-resistant highly strong diamond-like carbon layer.
EFFECT: provision of the operation in extreme conditions of open space due to the application of a thin substrate-envelope from a polymer composite material.
3 cl, 1 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to a monocrystal with a garnet-type structure to be used in optical communication and laser processing devices. This monocrystal is described by general formula (Tb3-xScx)(Sc2-yAly)Al3O12-z, where 0<x<0.1; 0≤y≤0.2; 0≤z≤0/.3.
EFFECT: translucent monocrystal that can inhibit cracking at cutting.
5 cl, 3 dwg, 1 tbl, 5 ex
SUBSTANCE: invention relates to an immersion liquid which can be used in optical instrument-making for investigating optical parameters of inorganic materials and optical components, including large, irregularly shaped articles. The immersion liquid for optical investigation contains 97-99 wt % meta-bis(meta-phenoxyphenoxy)benzene and 1-3 wt % 2-naphthol. To reduce viscosity and surface tension, the immersion liquid may further contain 0.1-3 wt % dibutyl sebacate per 100 wt % of said composition.
EFFECT: disclosed immersion liquid is nontoxic, has a good refraction index nD>1,6 and high adhesion to inorganic optical materials, which enables to deposit on the entire surface of the investigated substrate or part thereof a thin immersion layer and use thereof for effective quality control of large optical articles without immersion in a cell with an immersion liquid.
2 cl, 2 dwg, 2 tbl, 2 ex
FIELD: physics, optics.
SUBSTANCE: invention relates to visible light absorbers, particularly novel azo compound monomers, particularly suitable for use in materials for implantable ophthalmic lens materials. The ophthalmic device material includes an azo compound, a device forming acrylic monomer and a cross-linking agent. The ophthalmic device is made from the ophthalmic device material and is in the form of intraocular lenses, contact lenses, keratoprostheses and corneal inlays or rings.
EFFECT: azo compounds are suitable for use as monomers which absorb part of the visible light spectrum (about 380-495 nm).
17 cl, 6 dwg, 3 tbl
SUBSTANCE: free form ophthalmic lens comprises a first optical zone portion comprising multiple voxels of polymerised crosslinkable material containing a photoabsorptive component. The optical zone portion comprises a first area having a first refraction index and a second area having a second refraction index; and a second portion comprising a layered volume of crosslinkable material polymerised beyond the gel point of the crosslinkable material.
EFFECT: obtaining ophthalmic lenses with a free form surface and areas with different refraction indices, which enable to correct vision by changing the focal distance.
18 cl, 19 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to production of sandwiched materials used in thin-film instruments and devices. Proposed levelling film comprises levelling ply containing binding polymer resin and inorganic filler as components, at least, on one side of transparent polymer substrate. Note here that the number of foreign particles with mean diameter of 20-100 mcm on levelling air surface does not exceed 5 per m2.
EFFECT: decreased amount of linear defects at production of thin-film transistor on film surface.
3 cl, 1 tbl, 3 ex, 2 dwg
FIELD: physics, optics.
SUBSTANCE: group of inventions relates to producing a terbium aluminium garnet monocrystal which can be used as a Faraday rotator for optical insulators. In the terbium aluminium garnet monocrystal, a portion of aluminium is at least replaced with scandium and a portion of at least aluminium or terbium is replaced with at least one component selected from a group consisting of thulium, ytterbium and yttrium, wherein the garnet monocrystal has the general formula (Tb3-x-zSczMx) (Sc2-yMy) Al3O12 (1), where M represents at least one component selected from a group consisting of Tm, Yb and Y, and x, y and z satisfy the following relationship: 0<x+y≤0.30 and 0≤z≤0.30.
EFFECT: present monocrystal has a high light transmission factor in a wide wavelength range and a wide Faraday rotation angle with cracking-resistance.
8 cl, 3 dwg, 1 tbl, 12 ex
SUBSTANCE: invention relates to a curing composition for producing electrically insulating structural material for electrical or electronic components. The curing composition contains epoxy resin, a curing agent and a filler composition. The filler composition contains wollastonite and amorphous silicon dioxide. The surface of one of the fillers is treated with silane. A cured product is obtained by curing said curing composition.
EFFECT: invention enables to use said curing composition directly in the ceramic housing of a switching device and has high cracking resistance.
9 cl, 3 tbl, 2 ex