WO2018032874A1 - 一种紫外透明导电薄膜及其制造方法 - Google Patents

一种紫外透明导电薄膜及其制造方法 Download PDF

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WO2018032874A1
WO2018032874A1 PCT/CN2017/089370 CN2017089370W WO2018032874A1 WO 2018032874 A1 WO2018032874 A1 WO 2018032874A1 CN 2017089370 W CN2017089370 W CN 2017089370W WO 2018032874 A1 WO2018032874 A1 WO 2018032874A1
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indium oxide
transparent conductive
conductive film
growth
based transparent
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French (fr)
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王钢
卓毅
陈梓敏
范冰丰
马学进
李健
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Foshan Research Institute Of Sun Yat-Sen University
Sun Yat Sen University
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Foshan Research Institute Of Sun Yat-Sen University
Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/08—Reaction chambers; Selection of materials therefor
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/18—Epitaxial-layer growth characterised by the substrate
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides

Definitions

  • the invention provides a transparent conductive film and a manufacturing method thereof, and particularly relates to an ultraviolet transparent conductive film and a manufacturing method thereof.
  • Indium oxide doped especially tin-doped indium oxide (ITO)
  • ITO tin-doped indium oxide
  • I. Hamberg et al. reported in the Journal of Applied Physic that an indium oxide film obtained an optical band gap broadening of ⁇ 0.6 eV due to doping, and an optical band gap of ⁇ 4.3 eV was obtained (literature: Hamberg I, Granqvist CG. "Evaporated Sn-doped In2O3 films: Basic optical properties and applications to energy-efficient windows". Journal of Applied Physics.
  • the doped indium oxide thin film has an optical band gap of 3.75-4.3 eV, so that the spectral absorption edge is in the range of 290-330 nm, which can be used as a near-ultraviolet transparent conductive film, but if it is further extended to the deep ultraviolet region, the film is made. There is still a high transmittance at 300 nm, and the optical band gap needs to be further expanded to 4.4 eV or more.
  • methods for preparing indium oxide thin films mainly include magnetron sputtering, vacuum evaporation deposition, sol-gel method and spray pyrolysis.
  • JHPark et al. used magnetron sputtering to prepare tin-doped indium oxide thin films, which obtained an optical band gap of 4.17 eV and a resistivity of ⁇ 3 ⁇ 10 -4 ⁇ cm after annealing at 400 degrees (literature: JH Park, et al) "The effect of post-annealing on Indium Tin Oxide thin films by magnetron sputtering method", Applied Surface Science.
  • ITO film was also prepared by magnetron sputtering, obtained by Xu JIWEN et al.
  • the tin-doped indium oxide film has a low resistivity of 1.1 ⁇ 10 -4 ⁇ cm, but the optical band gap is only 3.95 eV (Document: Xu JW, et al. “Effect of growth temperature and coating cycles on structural, electrical, Optical properties and stability of ITO films deposited by magnetron sputtering". Materials Science in Semiconductor Processing. 2014; 21: 104 ⁇ 10.).
  • Evaporation deposition, solution method and other preparation methods are also facing similar problems: 1) Although the resistivity of the doped indium oxide thin film can reach ⁇ 5 ⁇ 10 -4 ⁇ cm, it can not stably obtain Eg ⁇ 4.1eV. Optical band gap; 2) The highest bandgap reported at present is only 4.3eV, which cannot meet the application of deep ultraviolet 300nm band; 3) The film quality and morphology cannot be precisely controlled (Document 1: J Du, et al.) Highly transparent and conductive indium tin oxide thin films for solar cells grown by reactive thermal evaporation at low temperature".Applied Physics a-Materials Science&Processing.2014;117(2):815 ⁇ 22.;Document 2:MJAlam,et al.” Optical and electrical properties of transparent conductive ITO thin films deposited by sol-gel process".Thin Solid Films.
  • MOCVD Metal organic chemical vapor deposition
  • PDSzkutnik published a report on the photoelectric properties of tin-doped indium oxide thin films grown using different organic source combinations, up to an optical band gap of ⁇ 4.2 eV, and disclosed the incorporation efficiency of different organic sources for tin and the optical properties of the films. There is a greater influence (PD Szkutnik, et al.
  • the present invention discloses an indium oxide-based transparent conductive film and a preparation method thereof, which have the advantages of being suitable for the ultraviolet-deep ultraviolet band and having a controllable topography.
  • An indium oxide-based transparent conductive film having an optical band gap in the range of 4.1 eV to 4.6 eV specifically, an indium oxide-based polycrystalline film. It mainly comprises a seed layer and a host layer (formed above the seed layer) formed on one side of the base material.
  • the overall thickness of the film is in the range of 20-500 nm, the spectral transmission area covers the entire near-ultraviolet band, the transmittance at 50 nm is more than 50%, and the resistivity is less than 5 ⁇ 10 -4 ⁇ cm. 5 ⁇ 10 -4 ⁇ cm.
  • a method for preparing an indium oxide-based transparent conductive film which is prepared by metal organic chemical vapor deposition (MOCVD) on a growth substrate, and specifically includes the following steps:
  • Growth substrate pretreatment chemically cleaning the surface of the growth substrate material and placing it in the MOCVD cavity;
  • seed layer growth a thin layer of seed crystals with the expected grain orientation on the substrate material, which is the basis for subsequent epitaxy;
  • the polycrystalline film is used to grow in a competitive growth mode, so that the film further evolves into a desired morphological structure during the growth process, and acts as a main conductor;
  • the organic indium source used in the indium oxide growth is trimethylindium
  • the oxygen source used is oxygen
  • the doping source used is tetrakis(dimethylamino)tin.
  • the trimethylindium flow rate is controlled within a range of 5 ⁇ 10 -6 to 2 ⁇ 10 ⁇ 4 mol/min, and the oxygen flow rate is controlled within a range of 1.3 ⁇ 10 ⁇ 2 to 2 ⁇ 10 ⁇ 1 mol/min.
  • the temperature of the tetrakis(dimethylamino) tin source bottle is controlled at 5 ° C
  • the source bottle pressure is 700 torr
  • the flow rate is controlled at 0 to 1000 sccm, or controlled within the same molar flow range.
  • the indium oxide-based transparent conductive film has a growth temperature in the range of 300 to 700 °C.
  • the indium oxide-based transparent conductive film has a growth gas pressure in the range of 3 to 100 torr.
  • the indium oxide-based transparent conductive film obtained by the method for preparing an indium oxide-based transparent conductive film of the present invention has an optical band gap of 4.1 eV to 4.6 eV, which satisfies the near-ultraviolet section as well as the excellent conductivity. Partial deep UV applications. It also precisely controls the growth quality and control morphology, and can form surfaces with different roughness from 1nm to 50nm according to different application requirements. At the same time, the MOCVD method is used for preparation, which is convenient for mass production and has a good application prospect in the field of ultraviolet photoelectric devices.
  • FIG. 1 is a schematic view showing the structure of an indium oxide-based transparent conductive film in an embodiment of the present invention
  • Fig. 4 is a X-ray diffraction test result of an indium oxide-based transparent conductive film in a specific example 1 of the present invention.
  • Fig. 5 is a scanning electron micrograph of a plane of an indium oxide-based transparent conductive film in a first embodiment of the present invention.
  • Fig. 6 is a scanning electron micrograph of a plane of an indium oxide-based transparent conductive film in a third embodiment of the present invention.
  • the indium oxide-based transparent conductive film produced by the method includes a seed layer and a host layer which are sequentially attached to one side of the base material. After testing, the indium oxide-based transparent conductive film has a low resistivity, a high near-ultraviolet transmittance, a spectral transmission region extending into the deep ultraviolet region, and the surface morphology of the film is controllable, and is suitable for ultraviolet-deep ultraviolet light.
  • transparent conductive film is a method for producing an indium oxide-based transparent conductive film to produce a novel indium oxide-based transparent conductive film which can be used in the ultraviolet-deep ultraviolet band.
  • the indium oxide-based transparent conductive film produced by the method includes a seed layer and a host layer which are sequentially attached to one side of the base material. After testing, the indium oxide-based transparent conductive film has a low resistivity, a high near-ultraviolet transmittance, a spectral transmission region extending into the deep ultraviolet region, and the surface morphology of the
  • the preliminary idea of the present invention is:
  • the organic metal trimethyl indium is used as the indium source
  • the organometallic tetrakis(dimethylamino) tin is used as the doping source
  • the purity of 99.9999% or more of oxygen is used as the oxygen source
  • the purity is 99.999% or more of argon gas.
  • the carrier gas and the growth protection atmosphere gradually grow an indium oxide-based transparent conductive film on the base material.
  • the sapphire substrate specifically used in the present embodiment is used as a base material. After the surface of the substrate material was cleaned by organic and inorganic acid and alkali, it was placed in a MOCVD reaction chamber, and the temperature was controlled at 600 °C and the pressure was 10 torr for 30 min.
  • the growth temperature was adjusted to be maintained at 530 ° C, the reaction chamber pressure was controlled at 9 torr, and argon gas was introduced as a protective atmosphere.
  • the organic metal trimethyl indium and oxygen are introduced, and the flow rates are controlled at 7 ⁇ 10 -5 mol/min and 9 ⁇ 10 -2 mol/min, respectively, and the organometallic tetrakis(dimethylamino) tin is doped, and the flow rate is controlled.
  • the source bottle temperature was 5 ° C, the bottle pressure was 440 torr, and the flow rate obtained at the flow rate of 350 sccm was the same, and a seed layer of 10 nm was grown on the surface of the base material.
  • the bulk layer is grown using the same growth conditions as the seed layer, and a bulk layer of 70 nm is grown on the basis of the seed layer.
  • Figure 2 is the test result of the indium oxide-based transparent conductive film Hall5500 tester in the present embodiment, as shown in the figure, the indium oxide-based transparent conductive film resistivity is less than 3.1 ⁇ 10 -4 ⁇ ⁇ cm;
  • FIG. 3 is a graph showing the transmission spectrum of the indium oxide-based transparent conductive film in this embodiment using a UV2550 spectrophotometer.
  • the indium oxide-based transparent conductive film has an optical band gap of -4.5 eV and is at 300 nm. There is still a penetration rate of 77.6%;
  • FIG. 4 is an X-ray diffraction pattern of the indium oxide-based transparent conductive film in the present embodiment, and it is understood that the obtained indium oxide-based film is a polycrystalline film having a specific (100) and (111) out-of-plane orientation. And has a good crystal quality.
  • FIG. 5 is a surface topography of the indium oxide-based transparent conductive film in the present embodiment, and the obtained film has a grain size of 50-100 nm, and the film has a rough surface morphology.
  • the present embodiment shows that the indium oxide-based transparent conductive film obtained by the MOCVD technique has an optical band gap of up to 4.5 eV in addition to excellent electrical conductivity, and can precisely control the topography and rough surface. Has a higher transmittance.
  • quartz is used as the base material, and the preparation steps are the same as in the first embodiment.
  • the finally obtained indium oxide-based transparent conductive film has a resistivity of less than 4.9 ⁇ 10 -4 ⁇ cm and has an optical band gap of 4.33 eV, a transmittance of 65.7% at a wavelength of 300 nm, and a rough film. Surface topography.
  • the sapphire is used as the base material in this embodiment, and is different from the first embodiment in that:
  • the temperature is controlled at 530 ° C
  • the pressure is controlled at 9 torr
  • argon gas is introduced as a protective atmosphere.
  • the organic metal trimethyl indium and oxygen were introduced, and the flow rates were controlled at 1.2 ⁇ 10 -5 mol/min and 1.6 ⁇ 10 -2 mol/min, respectively, and a seed layer of 20 nm was grown on the surface of the base material.
  • the temperature is controlled at 565 ° C, the pressure is controlled at 9 torr, and argon gas is introduced as a protective atmosphere.
  • the organic metal trimethyl indium and oxygen were introduced, and the flow rates were controlled at 2.5 ⁇ 10 -5 mol/min and 1.8 ⁇ 10 -1 mol/min, respectively, and the organometallic tetrakis(dimethylamino) tin was incorporated, and the flow rate was controlled.
  • the source bottle temperature was 5 ° C
  • the bottle pressure was 700 torr
  • the flow rate was 320 sccm
  • the molar flow rate was the same, and the 100 nm bulk layer was grown on the seed layer.
  • the indium oxide-based transparent conductive film obtained in the present embodiment has an optical band gap of 3.2 ⁇ 10 ⁇ 4 ⁇ cm and 4.13 eV, and FIG. 5 is a surface topography of the indium oxide-based transparent conductive film in the embodiment. It can be seen that the obtained indium oxide-based transparent conductive film has a flat surface.

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Abstract

一种氧化铟基透明导电薄膜，包括顺序附着在基底材料一侧表面的籽晶层和主体层。该氧化铟基透明导电薄膜的制备方法主要通过金属有机化学气相沉积的方式，以有机金属三甲基铟作为铟源、高纯氧气作为氧源，四(二甲氨基)锡作为掺杂源制备获得，具体包括如下步骤：基底材料预处理；籽晶层生长；主体层生长。采用该氧化铟基透明导电薄膜的制造方法获得的氧化铟基透明导电薄膜除了能满足优良的电导率以外，光谱透射区域延伸到深紫外波段，具有4.1～4.6eV的光学带隙，且可以精准控制表面形貌，适用于作为近紫外-深紫外波段的透明导电薄膜。

Description

一种紫外透明导电薄膜及其制造方法 技术领域
本发明设计半导体技术领域，具体涉及一种透明导电薄膜及制造方法，特别涉及一种紫外透明导电薄膜及其制造方法。
背景技术
传统透明导电薄膜具有较高的可见光透过率和接近金属的导电性而被广泛应用于平板显示、太阳能电池、发光器件、光电探测器等领域，应用前景广阔。目前，随着紫外光电器件的迅速发展，正迫切需要一种紫外透明导电薄膜作为紫外光电器件的透明电极，而传统透明导电薄膜却往往难以透过波长小于300nm的紫外光。因此，如何将透明导电薄膜的光谱透射区域扩展到深紫外光是透明导电薄膜研究和应用的一个重要难题。
掺杂氧化铟，特别是锡掺杂氧化铟(Indium Tin Oxide,ITO)，具有透光率高、导电性好、耐磨性好、化学稳定性高、衬底附着性强及硬度较高等优点，是目前使用最广泛，工艺最成熟的透明导电薄膜。早在1986年，I.Hamberg等人在Journal of Applied Physic上报道了氧化铟薄膜由于掺杂引起获得～0.6eV的光学带隙展宽，可以获得～4.3eV的光学带隙(文献：Hamberg I,Granqvist CG."Evaporated Sn‐doped In2O3 films:Basic optical properties and applications to energy‐efficient windows".Journal of Applied Physics.1986；60(11):R123‐R160.)。掺杂氧化铟薄膜所具有的3.75～4.3eV的光学带隙使得其光谱吸收边处在290～330nm范围内，可以用作近紫外透明导电薄膜，但若要进一步扩展到深紫外区域，使薄膜于300nm处仍有较高透射率，光学带隙需要进一步扩展至4.4eV以上。
目前制备氧化铟薄膜的方法主要包括磁控溅射法、真空蒸发沉积法，溶胶‐凝胶法和喷雾热解法等。如J.H.Park等人采用磁控溅射的方法制备掺锡氧化铟薄膜，经过400度退火后获得4.17eV的光学带隙以及＜3×10-4Ω·cm电阻率(文献：JH Park,et al.“The effect of post‐annealing on Indium Tin Oxide thin films by magnetron sputtering method”,Applied Surface Science.2014；307:388‐92.)；同样采用磁控溅射方法制备ITO薄膜，Xu JIWEN等人获得的掺锡氧化铟薄膜具有 1.1×10-4Ω·cm的低电阻率，但光学带隙却只有3.95eV(文献：Xu JW,et al.“Effect of growth temperature and coating cycles on structural,electrical,optical properties and stability of ITO films deposited by magnetron sputtering”.Materials Science in Semiconductor Processing.2014；21:104‐10.)。蒸发沉积，溶液法等其他制备方法也面临着类似的难题：1)虽然获得的掺杂氧化铟薄膜电阻率均能够达到ρ＜5×10-4Ω·cm，但不能稳定获得Eg～4.1eV的光学带隙；2)目前报道最高的带隙只能达到4.3eV，不能满足深紫外300nm波段的应用；3)不能精准控制薄膜质量和形貌结构(文献1：J Du,et al."Highly transparent and conductive indium tin oxide thin films for solar cells grown by reactive thermal evaporation at low temperature".Applied Physics a‐Materials Science&Processing.2014；117(2):815‐22.；文献2：M.J.Alam,et al."Optical and electrical properties of transparent conductive ITO thin films deposited by sol–gel process".Thin Solid Films.2000；377–378:455‐459.；文献3：O.Malik,et al."Comparison of tin‐doped indium oxide films fabricated by spray pyrolysis and magnetron sputtering".Crystal Research and Technology.2015；50(7):516‐521.)。
为了进一步扩展光学带隙，需要在保证薄膜结晶质量的同时进一步提高载流子浓度。金属有机化学气相沉积(MOCVD)由于具有可量产性，外延生长半导体薄膜的结晶质量高，生长模式和界面可控，是制备高质量氧化铟基透明导电薄膜的有效手段。P.D.Szkutnik发表文献报道了使用不同有机源组合生长的掺锡氧化铟薄膜的光电性能，最高获得～4.2eV的光学带隙，并披露了不同的有机源对锡并入效率以及薄膜的光电性能都有较大影响(PD Szkutnik,et al."Study of the functional properties of ITO grown by metalorganic chemical vapor deposition from different indium and tin precursors".Journal of Alloys and Compounds.2014；603:268‐273.)。综上所述，急需探索出一种高效的反应物组合以及开发一种适用于生长紫外‐深紫外氧化铟基透明导电薄膜的MOCVD生长工艺。
发明内容
为克服上述所述的至少一种缺陷，本发明公开一种氧化铟基透明导电薄膜及其制备方法，其具有适用于紫外‐深紫外波段且形貌结构可控的优点。
为了实现上述目的，本发明采用如下技术方案：
一种具有4.1eV～4.6eV范围的光学带隙的氧化铟基透明导电薄膜，具体来说是一种氧化铟基多晶薄膜。其主要包括在基底材料一侧形成的籽晶层和主体层(形成与籽晶层之上)。薄膜整体厚度在20‐500nm范围内，光谱透射区域覆盖整个近紫外波段，300nm处有50％以上的透过率，且电阻率小于5×10-4Ω·cm。5×10-4Ω·cm。
一种氧化铟基透明导电薄膜的制备方法，它是在生长基底上通过金属有机化学气相沉积(MOCVD)制备而成的，具体包括如下步骤：
1)生长基底预处理：对生长基底材料的表面进行化学清洗，并放入MOCVD腔体；
2)籽晶层生长：基底材料上生长出预期晶粒取向的籽晶薄层，为后续的外延做基础；
3)主体层生长：在籽晶层的基础上，利用多晶薄膜竞争生长模式进行生长，，使得薄膜在生长过程进一步演化成为所需要的形貌结构，并充当主体导电的作用；
优选地，所述氧化铟生长中使用的有机铟源为三甲基铟，所使用的氧源是氧气，所使用的掺杂源为四(二甲氨基)锡。
优选地，所述三甲基铟流量控制在5×10-6～2×10-4mol/min范围内，氧气流量控制在1.3×10-2～2×10-1mol/min范围内。
优选地，所述四(二甲氨基)锡源瓶温度控制在5℃，源瓶压力700torr，流量控制在0～1000sccm，或控制在同样的摩尔流量范围内。
优选地，所述氧化铟基透明导电薄膜生长温度在300～700℃范围内。
优选地，所述氧化铟基透明导电薄膜生长气压在3‐100torr范围内。
采用本发明的氧化铟基透明导电薄膜的制备方法得到的氧化铟基透明导电薄膜除了满足优良的导电性以外，还具有宽达4.1eV～4.6eV的光学带隙，可以满足近紫外全段以及部分深紫外波段的应用需求。还能精准控制生长质量和控制形貌，根据不同的应用需求可以形成粗糙度为1nm～50nm不同粗糙度的表面。同时，采用MOCVD方法进行制备，便于量产，在紫外光电器件领域具有良好的应用前景。
附图说明
图1是本发明具体实施方式中的氧化铟基透明导电薄膜结构示意图
图2是本发明具体实施例一中氧化铟基透明导电薄膜的霍尔测试结果。
图3是本发明具体实施例一中氧化铟基透明导电薄膜的透射谱测试结果。
图4是本发明具体实施例一中氧化铟基透明导电薄膜的X射线衍射测试结果。
图5是本发明具体实施例一中氧化铟基透明导电薄膜平面的扫描电镜图。
图6是本发明具体实施例三中氧化铟基透明导电薄膜平面的扫描电镜图。
具体实施方式
附图仅用于示例性说明，不能理解为对本专利的限制；为了更好说明本实施例，附图某些部件会有省略、放大或缩小，并不代表实际产品的尺寸；对于本领域技术人员来说，附图中某些公知结构及其说明可能省略是可以理解的。附图中描述位置关系仅用于示例性说明，不能理解为对本专利的限制。
实施例一
本具体实施方式的目的的是提供一种制造氧化铟基透明导电薄膜的方法，来制造一种紫外‐深紫外波段可以用的新型氧化铟基透明导电薄膜。该方法制造出的氧化铟基透明导电薄膜如图一所示，包括依次附着在基底材料一侧的籽晶层和主体层。经过测试，该氧化铟基透明导电薄膜具有较低的电阻率，较高的近紫外透过率，光谱透过区延伸到深紫外波段，且薄膜表面形貌可控，适用于紫外‐深紫外透明导电薄膜的应用。
为了获得上述氧化铟基透明导电薄膜，本发明的初步思路是：
利用现有MOCVD设备，采用有机金属三甲基铟作为铟源，有机金属四(二甲氨基)锡作为掺杂源，纯度99.9999％以上的氧气作为氧源，纯度为99.999％以上的氩气作为载气和生长保护气氛，在基底材料上逐步生长出氧化铟基透明导电薄膜。
制备所述氧化铟基透明导电薄膜的具体步骤为：
1.基底材料预处理
本实施例中具体使用的蓝宝石衬底作为基底材料。对基底材料表面进行有机和无机酸碱清洗后，放入MOCVD反应腔内，控制温度在600度，压力10torr处理30min。
2.籽晶层生长
调整生长温度保持在530℃，反应腔气压控制在9torr，通入氩气作为保护气氛的情况下。通入有机金属三甲基铟和氧气，流量分别控制在7×10-5mol/min和9×10-2mol/min，并掺入有机金属四(二甲氨基)锡，流量控制为与源瓶温度5℃，瓶压440torr，流量350sccm时获得的摩尔流量相同，在基底材料表面生长出10nm的籽晶层。
3.主体层生长
本实施例中主体层生采用与籽晶层相同的生长条件，在籽晶层的基础上生长处70nm的主体层。
下面将结合附图对本实施例作进一步说明：
1)图2为本实施例中氧化铟基透明导电薄膜Hall5500测试仪测试结果，由图可见，该氧化铟基透明导电薄膜电阻率低于3.1×10-4Ω·cm；
2)图3为使用UV2550分光光度计测试本实施例中氧化铟基透明导电薄膜的透过谱，由图可见，该氧化铟基透明导电薄膜具有～4.5eV的光学带隙，且在300nm处仍有77.6％的透过率；
3)图4为本实施例中氧化铟基透明导电薄膜的X射线衍射图谱，由图可知，所获得的氧化铟基薄膜是具有特定(100)和(111)面外取向的多晶薄膜，且具有较好的结晶质量。
4)图5为本实施例中氧化铟基透明导电薄膜的表面形貌，可见获得的薄膜晶粒大小在50‐100nm，且薄膜具有较粗糙表面形貌。
综上所述，本实施例表明利用MOCVD技术得到的氧化铟基透明导电薄膜除了满足优良的导电性以外，具有宽达4.5eV的光学带隙，还能精准控制形貌结构，粗糙表面使其具有更高的透过率。
实施例二
本实施例中采用石英作为基底材料，制备步骤与实施例一相同。最后获得的氧化铟基透明导电薄膜电阻率低于4.9×10-4Ω·cm，且具有宽达4.33eV的光学带隙，与波长为300nm处具有65.7％的透过率，且薄膜具有粗糙的表面形貌。
实施例三
本实施例中采用蓝宝石作为基底材料，与实施例一的不同之处在于：
籽晶层生长时，温度控制在530℃，压力控制在9torr，通入氩气作为保护气氛的情况下。通入有机金属三甲基铟和氧气，流量分别控制在1.2×10-5mol/min和1.6×10-2mol/min，在基底材料表面生长出20nm的籽晶层。
主体层生长时，温度控制在565℃，压力控制在9torr，通入氩气作为保护气氛的情况下。通入有机金属三甲基铟和氧气，流量分别控制在2.5×10-5mol/min和1.8×10-1mol/min，并掺入有机金属四(二甲氨基)锡，流量控制为与源瓶温度5℃，瓶压700torr，流量320sccm时获得的摩尔流量相同，在籽晶层上生长100nm主体层。
经测试，本实施例中获得的氧化铟基透明导电薄膜具有3.2×10-4Ω·cm以及4.13eV的光学带隙，图5是本实施例中氧化铟基透明导电薄膜的表面形貌，可见获得的氧化铟基透明导电薄膜具有平整的表面。

Claims (9)

  1. 一种氧化铟基透明导电薄膜，其包括书序附着在基底材料一侧表面的氧化铟籽晶层和氧化铟主体层。
  2. 如权利要求1所述的一种氧化铟透明导电薄膜，其特征在于：所述的氧化铟透明导电薄膜的掺杂源为锡，掺杂原子与锌的原子比为1％‐25％。
  3. 如权利要求1所述的一种氧化铟基透明导电薄膜，其特征在于：具有4.1～4.6eV的光学带隙。
  4. 如权利要求2,3所述的一种氧化铟基透明导电薄膜，其特征在于：采用MOCVD外延生长获得。
  5. 一种氧化铟基透明导电薄膜的制备方法，主要采用金属有机化学气相沉积方法制备，具体包括如下步骤：
    1)生长基底预处理：对生长基底材料的表面进行化学清洗和炉内高温处理；
    2)籽晶层生长：基底材料上生长出预期晶粒取向的籽晶薄层；
    3)主体层生长：在籽晶层的基础上利用多晶薄膜竞争生长模式进行生长，获得所需表面形貌的主体层；
  6. 如权利要求5所述的一种氧化铟基透明导电薄膜的制备方法，其特征在于：步骤1)中所述化学清洗包括有机清洗和无机酸碱清洗处理，所述炉内高温处理是指在MOCVD内部保持300℃至900℃、压力3至100torr高温处理1至60分钟。
  7. 如权利要求5所述的一种氧化铟基透明导电薄膜的制备方法，其特征在于：步骤2)和3)中所述氧化铟层生长使用的有机金属源为三甲基铟，氧源为氧气，掺杂源采用四(二甲氨基)锡。
  8. 如权利要求5所述的一种氧化铟基透明导电薄膜的制备方法，其特征在于：步骤2)中所述氧化铟籽晶层生长温度在200℃至800℃,生长压力在3‐100torr范围内，厚度在2‐20nm范围内。
  9. 如权利要求5所述的一种氧化铟基透明导电薄膜的制备方法，其特征在于：步骤3)中所述氧化铟主体层生长温度在300℃至900℃，生长压力在3‐100torr范围内，厚度10nm‐1um范围内。
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