WO2012129757A1 - 多元素掺杂氧化锌薄膜及其制备方法和应用 - Google Patents

多元素掺杂氧化锌薄膜及其制备方法和应用 Download PDF

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WO2012129757A1
WO2012129757A1 PCT/CN2011/072144 CN2011072144W WO2012129757A1 WO 2012129757 A1 WO2012129757 A1 WO 2012129757A1 CN 2011072144 W CN2011072144 W CN 2011072144W WO 2012129757 A1 WO2012129757 A1 WO 2012129757A1
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zinc oxide
doped zinc
oxide film
powder
element doped
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PCT/CN2011/072144
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English (en)
French (fr)
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周明杰
王平
陈吉星
黄辉
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海洋王照明科技股份有限公司
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Priority to CN2011800673519A priority Critical patent/CN103403213A/zh
Priority to US14/002,589 priority patent/US20130334688A1/en
Priority to PCT/CN2011/072144 priority patent/WO2012129757A1/zh
Priority to EP11862536.7A priority patent/EP2690192B1/en
Priority to JP2014500228A priority patent/JP5879427B2/ja
Publication of WO2012129757A1 publication Critical patent/WO2012129757A1/zh

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    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
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    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the invention belongs to the field of semiconductor photoelectric material preparation, and particularly relates to a preparation method of a multi-element doped zinc oxide film and a film and application thereof.
  • ITO film tin-doped In 2 O 3
  • ITO film is a transparent conductive film material with excellent comprehensive photoelectric performance and wide application, but indium is toxic, expensive, poor in stability, and there are problems such as indium diffusion leading to device performance degradation. People are trying to find a low price and performance. Excellent ITO replacement material.
  • the doped zinc oxide system is a hot research topic at home and abroad. Zinc oxide is cheap and non-toxic. After being doped with elements such as aluminum, gallium, indium, fluorine and silicon, the electrical and optical properties comparable to those of ITO can be obtained. Become the most competitive transparent conductive film material.
  • the gallium-doped zinc oxide film has problems such as surface and grain boundary oxygen adsorption leading to a decrease in electrical properties, and the aluminum-doped zinc oxide has a tendency to overflow the surface due to oxygen atoms, so that the stability is not high, and the like.
  • the transparent conductive film is prepared by magnetron sputtering method, which has the advantages of high deposition rate, good film adhesion, easy control and large area deposition. It has become the most researched, matured and widely used in industrial production. Item method. However, ordinary domestic magnetron sputtering equipment generally can only produce polycrystalline thin films with poor crystal quality, and it is necessary to heat the substrate or post-high temperature annealing treatment to improve crystallization and reduce resistivity. To achieve film preparation on an organic flexible substrate, the deposition temperature should not be too high, which would otherwise cause severe deformation of the substrate.
  • the technical problem to be solved by the present invention is to overcome the defects of the prior art, and to provide a preparation method of a multi-element doped zinc oxide film and a film and application thereof.
  • Another object of the embodiments of the present invention is to provide a multi-element doped zinc oxide film obtained by the above method for preparing a multi-element doped zinc oxide film.
  • Embodiments of the present invention are achieved by the first aspect of the present invention, a method for preparing a multi-element doped zinc oxide film, and a film and application thereof, comprising the steps of:
  • the Ga 2 O 3 powder, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder are mixed and sintered as a target, wherein the Ga 2 O 3 powder accounts for 0.5% to 10% of the total mass.
  • the Al 2 O 3 powder accounts for 0.5% to 5% of the total mass
  • the SiO 2 powder accounts for 0.5% to 1.5% of the total mass
  • the balance is ZnO powder;
  • the target is placed in a magnetron sputtering chamber, vacuumed, and the working pressure is set to 0.2 Pa to 5 Pa, and a mixed gas of inert gas and hydrogen gas is introduced, the flow rate of the mixed gas is 15 sccm to 25 sccm, and the sputtering power is 40 W. 200 W, a multi-element doped zinc oxide film was sputtered on the substrate.
  • a multi-element target material is prepared, and a multi-element doped zinc oxide film is obtained by magnetron sputtering, which has the advantages of high deposition rate, good film adhesion, easy control and large area deposition. Further, multi-element doping can achieve a reduction in electrical resistance and improve photoelectric performance. Further, a mixed gas of an inert gas and a hydrogen gas passed through the sputtering chamber is used as a working gas, so that a low-resistance doped zinc oxide thin film can be obtained at a low temperature.
  • FIG. 1 is a flow chart showing a method of preparing a multi-element doped zinc oxide film according to an embodiment of the present invention
  • FIG. 2 is a transmission spectrum diagram of a multi-element doped zinc oxide film according to Embodiment 1 of the present invention in an ultraviolet-visible wavelength range;
  • Example 3 is a graph showing the resistance change of the multi-element doped zinc oxide film prepared in Example 1 of the present invention after 48 hours of use at different use temperatures.
  • a method for preparing a multi-element doped zinc oxide film includes the following steps:
  • S01 mixing Ga 2 O 3 powder, Al 2 O 3 powder, SiO 2 powder, and ZnO powder, and sintering as a target, wherein the Ga 2 O 3 powder accounts for 0.5% to 10% of the total mass. %, the Al 2 O 3 powder accounts for 0.5% to 5% of the total mass, and the SiO 2 powder accounts for 0.5% to 1.5% of the total mass;
  • S02 loading the target into a magnetron sputtering chamber, evacuating, setting a working pressure of 0.2 Pa to 5 Pa, and introducing a mixed gas of inert gas and hydrogen, and the mixed gas flow rate is 15 From scm to 25 sccm, the sputtering power is 40 W to 200 W, and a multi-element doped zinc oxide film is sputtered on the substrate.
  • a Ga 2 O 3 powder, an Al 2 O 3 powder, an SiO 2 powder, and a ZnO powder are mixed, wherein ZnO is a matrix.
  • the powder was sintered at a temperature of 900 ° C to 1300 ° C to obtain a sputtering target.
  • the Ga 2 O 3 powder accounts for 2% to 4% of the total mass
  • the Al 2 O 3 powder accounts for 0.8% to 1.5% of the total mass
  • the SiO 2 powder accounts for 0.6% of the total mass. % ⁇ 1%.
  • Aluminum and gallium can improve the electrical conductivity of zinc oxide. Silicon can stabilize the conductivity and stabilize the chemical properties.
  • Gallium doping can also increase the band gap of the film and expand the wavelength range of light transmission.
  • a sputtering of the multi-element doped zinc oxide film may be selected from a quartz substrate or an organic flexible substrate.
  • Organic flexible substrates include: polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), polyether sulfone (PES), and the like.
  • PET polyethylene terephthalate
  • PC polycarbonate
  • PEN polyethylene naphthalate
  • PES polyether sulfone
  • the flexible substrate has the advantages of good flexibility and low cost, but due to its poor flatness and low melting point, the preparation process of many transparent conductive films is not suitable for selecting a flexible substrate.
  • the substrate is passed through cooling water to control the temperature below 100 °C.
  • the substrate was ultrasonically washed with absolute ethanol and deionized water before use and dried with high purity nitrogen.
  • the distance between the target and the substrate is preferably from 50 mm to 90 mm.
  • the vacuum is evacuated, and the vacuum of the chamber is pumped to 1.0 ⁇ 10 ⁇ 3 Pa to 1.0 ⁇ 10 ⁇ 5 Pa or more, preferably 6.0 ⁇ 10 ⁇ 4 Pa by a mechanical pump or a molecular pump. .
  • the process conditions are very important.
  • the working gas in the sputtering chamber is a mixed gas of an inert gas and hydrogen gas, wherein the molar volume percentage of hydrogen is from 1% to 5%, preferably, the molar percentage of hydrogen is from 3% to 6%, more preferably, the molar ratio of hydrogen The volume percentage is 5%.
  • the gas flow rate is preferably 18 sccm to 22 sccm
  • the working pressure is preferably 0.8 Pa to 1.2 Pa
  • the sputtering power is preferably 80 W to 120 W.
  • the thickness of the film is generally from 150 nm to 500 nm.
  • the embodiment of the invention further provides a multi-element doped zinc oxide film prepared by the method for preparing the multi-element doped zinc oxide film, which is used below 0° C. to 120° C., and the resistance change rate is less than 15%.
  • the preparation method of the multi-element doped zinc oxide thin film provided by the embodiment of the invention adopts the magnetron sputtering method to achieve the maximum reduction of the sheet resistance, and further, the doping makes the zinc oxide have stable electrical and chemical properties, and the film strip The gap width is increased while maintaining high transmittance in the visible region. Moreover, a mixed gas of an inert gas and a hydrogen gas is used as a working gas in the sputtering process, and a low-resistance multi-element doped zinc oxide film can be prepared at a low temperature.
  • the Ga 2 O 3 powder, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder are all mixed, wherein the Ga 2 O 3 powder accounts for 1.5% of the total mass, and the Al 2 O 3 powder accounts for the total mass. 2%, SiO 2 powder accounts for 1% of the total mass, ZnO powder accounts for 95.5% of the total mass.
  • the ceramic target of 50 ⁇ 2 mm is sintered at a high temperature of 1250 ° C, and the target is vacuumed. Inside the cavity. Then, the PET substrate was ultrasonically washed with absolute ethanol and deionized water, and dried with high purity nitrogen gas, and placed in a vacuum chamber. Set the distance between the target and the substrate to 60 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 6.0 ⁇ 10 -4 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 3% (molar to volume ratio), and the mixture is mixed.
  • the gas flow rate was 20 sccm and the pressure was adjusted to 1.0 Pa.
  • the sputtering power was 100 W and the deposition of the film was started.
  • the visible light average transmittance of the multi-element doped zinc oxide film was greater than 85% and the specific resistance was 9.3 ⁇ 10 -4 ⁇ •cm.
  • the Ga 2 O 3 powder, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder are all mixed, wherein the Ga 2 O 3 powder accounts for 2.5% of the total mass, and the Al 2 O 3 powder accounts for the total mass. 2%, SiO 2 powder accounts for 1% of the total mass, ZnO powder accounts for 94.5% of the total mass.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 6.0 ⁇ 10 -4 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 5% (molar to volume ratio), and the mixture is mixed.
  • the gas flow rate was 20 sccm and the pressure was adjusted to 3.0 Pa.
  • the sputtering power was 120 W and the deposition of the film was started.
  • the visible light average transmittance of the multi-element doped zinc oxide film was greater than 78% and the specific resistance was 8 ⁇ 10 -4 ⁇ •cm.
  • the Ga 2 O 3 powder, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder are all mixed, wherein the Ga 2 O 3 powder accounts for 2% of the total mass, and the Al 2 O 3 powder accounts for the total mass. 2%, SiO 2 powder accounts for 1% of the total mass, ZnO powder accounts for 95% of the total mass.
  • it is sintered at a high temperature of 1250 ° C into a ceramic target of 50 ⁇ 2 mm, and the target is vacuumed. Inside the cavity. Then, the PET substrate was ultrasonically washed with absolute ethanol and deionized water, and dried with high purity nitrogen gas, and placed in a vacuum chamber. Set the distance between the target and the substrate to 60 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 6.0 ⁇ 10 -4 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 2% (molar to volume ratio), and the mixture is mixed.
  • the gas flow rate was 20 sccm and the pressure was adjusted to 2.0 Pa.
  • the sputtering power was 100 W and the deposition of the film was started.
  • the visible light average transmittance of the multi-element doped zinc oxide film was greater than 80% and the specific resistance was 9.9 ⁇ 10 -4 ⁇ •cm.
  • the Ga 2 O 3 powder, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder are all mixed, wherein the Ga 2 O 3 powder accounts for 5% of the total mass, and the Al 2 O 3 powder accounts for the total mass. 2%, SiO 2 powder accounts for 1% of the total mass, ZnO powder accounts for 92% of the total mass.
  • it is sintered at a high temperature of 1250 ° C into a ceramic target of 50 ⁇ 2 mm, and the target is filled into a vacuum. Inside the cavity. Then, the PET substrate was ultrasonically washed with absolute ethanol and deionized water, and dried with high purity nitrogen gas, and placed in a vacuum chamber. Set the distance between the target and the substrate to 60 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 6.0 ⁇ 10 -4 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 1% (molar to volume ratio), and the mixture is mixed.
  • the gas flow rate was 20 sccm and the pressure was adjusted to 5.0 Pa.
  • the sputtering power was 90 W and the deposition of the film was started.
  • the visible light average transmittance of the multi-element doped zinc oxide film was greater than 88% and the resistivity was 2.5 ⁇ 10 -3 ⁇ •cm.
  • the Ga 2 O 3 powder, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder are all mixed, wherein the Ga 2 O 3 powder accounts for 10% of the total mass, and the Al 2 O 3 powder accounts for the total mass. 2%, SiO 2 powder accounts for 1% of the total mass, ZnO powder accounts for 87% of the total mass.
  • it is sintered at a high temperature of 1250 ° C into a ceramic target of 50 ⁇ 2 mm, and the target is vacuumed. Inside the cavity. Then, the PET substrate was ultrasonically washed with absolute ethanol and deionized water, and dried with high purity nitrogen gas, and placed in a vacuum chamber. Set the distance between the target and the substrate to 60 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 6.0 ⁇ 10 -4 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 2.5% (molar to volume ratio), and the mixture is mixed.
  • the gas flow rate was 20 sccm and the pressure was adjusted to 0.5 Pa.
  • the deposition power was 80 W and the deposition of the film was started.
  • the visible light average transmittance of the multi-element doped zinc oxide film was greater than 82% and the specific resistance was 3.3 ⁇ 10 -3 ⁇ •cm.
  • the Ga 2 O 3 powder, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder are all mixed, wherein the Ga 2 O 3 powder accounts for 0.5% of the total mass, and the Al 2 O 3 powder accounts for the total mass. 0.5%, SiO 2 powder accounts for 0.5% of the total mass, ZnO powder accounts for 98.5% of the total mass.
  • 900 ° C high temperature sintering into a 50 ⁇ 2 mm ceramic target the target is vacuumed Inside the cavity.
  • the PET substrate was ultrasonically washed with absolute ethanol and deionized water, and dried with high purity nitrogen gas, and placed in a vacuum chamber. Set the distance between the target and the substrate to 70 mm.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 6.0 ⁇ 10 -4 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 8% (molar to volume ratio), and the mixture is mixed.
  • the gas flow rate was 15 sccm and the pressure was adjusted to 1.0 Pa.
  • the deposition power was 40 W and the deposition of the film was started.
  • the visible light average transmittance of the multi-element doped zinc oxide film was greater than 72% and the resistivity was 9.2 ⁇ 10 -3 ⁇ •cm.
  • the Ga 2 O 3 powder, the Al 2 O 3 powder, the SiO 2 powder, and the ZnO powder are all mixed, wherein the Ga 2 O 3 powder accounts for 0.5% of the total mass, and the Al 2 O 3 powder accounts for the total mass. 5%, SiO 2 powder accounts for 1.5% of the total mass, ZnO powder accounts for 93% of the total mass.
  • the mechanical pump and the molecular pump are used to pump the vacuum of the chamber to 6.0 ⁇ 10 -4 Pa, and a mixed gas of argon gas and hydrogen gas is introduced into the vacuum chamber, wherein the hydrogen content is 10% (molar ratio), the mixed gas
  • the flow rate was 15 sccm and the pressure was adjusted to 1.0 Pa.
  • the sputtering power was 200 W and the deposition of the film was started.
  • the visible light average transmittance of the multi-element doped zinc oxide film was greater than 70% and the specific resistance was 8.2 ⁇ 10 -3 ⁇ •cm.
  • FIG. 2 is a transmission spectrum of a multi-element doped zinc oxide film of PET prepared as a substrate in the ultraviolet-visible wavelength range of the present invention, and it can be seen that the visible light transmittance is greater than 85%.
  • 3 is a graph showing the resistance change of the multi-element doped zinc oxide film prepared in Example 1 at different use temperatures for 48 hours.
  • the rate of change of resistance is the new sheet resistance R1 obtained by the four-probe test after heating the multi-element doped zinc oxide film for 48 hours at the illustrated temperature.
  • the figure shows that the resistance change rate of less than 15% at 48 ° C for 48 hours has reached the performance standard for industrial production.

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Description

[根据细则37.2由ISA制定的发明名称]　多元素掺杂氧化锌薄膜及其制备方法和应用 技术领域
本发明属于半导体光电材料制备领域，具体涉及一种多元素掺杂氧化锌薄膜的制备方法及其制备的薄膜和应用。
 背景技术
近几年，柔性衬底透明导电膜的研究引起了世界各国的关注，因为柔性衬底透明导电膜应用前景可观，它不但具有玻璃衬底透明导电膜的特点，而且还有许多独特的优点，如可挠曲、重量轻、耐冲击、易于大面积生产、便于运输等。在柔性发光器件、塑料液晶显示器和塑料衬底的太阳电池等中有广泛的应用前景。
目前在应用上绝大多数的透明导电薄膜材料都是使用掺锡氧化铟（Sn-doped In2O3，简称ITO薄膜）。虽然ITO薄膜是目前综合光电性能优异、应用最为广泛的一种透明导电薄膜材料，但是铟有毒，价格昂贵，稳定性差，存在铟扩散导致器件性能衰减等问题，人们力图寻找一种价格低廉且性能优异的ITO替换材料。其中，掺杂氧化锌体系是国内外研究的热点，氧化锌廉价，无毒，经铝、镓、铟、氟和硅等元素的掺杂后可以得到同ITO相比拟的电学和光学性能，已成为最具竞争力的透明导电薄膜材料。但是，对于单一元素掺杂的氧化锌薄膜，生产中不容易制备得到低电阻的薄膜，而且导电和化学稳定性较差。例如，掺镓氧化锌薄膜存在表面和晶粒间界氧吸附导致电学性能下降等问题，掺铝氧化锌由于氧原子有溢出表面的趋势，从而稳定性不高，等等。
采用磁控溅射方法制备透明导电薄膜，具有沉积速率高、薄膜附着性好、易控制并能实现大面积沉积等优点，因而成为当今工业化生产中研究最多、工艺最成熟和应用最广的一项方法。但是普通国产的磁控溅射设备，一般只能制备出结晶质量较差的多晶的薄膜，需要通过加热衬底或后高温退火处理才能提高结晶，降低电阻率。要实现在有机柔性衬底上制备薄膜，沉积温度不能过高，否则会引起衬底的严重变形。
 技术问题
本发明所要解决的技术问题在于克服现有技术之缺陷，提供一种多元素掺杂氧化锌薄膜的制备方法及其制备的薄膜和应用。
本发明实施例的另一目的在于提供上述多元素掺杂氧化锌薄膜的制备方法获得的多元素掺杂氧化锌薄膜。
本发明实施例的又一目的在于提供上述多元素掺杂氧化锌薄膜在半导体光电器件中的应用。
 技术解决方案
本发明实施例是这样实现的，第一方面提供多元素掺杂氧化锌薄膜的制备方法及其制备的薄膜和应用，其包括如下步骤：
将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体混合，烧结作为靶材，其中，所述Ga2O3粉体占总质量的0.5%～10%，所述Al2O3粉体占总质量的0.5%～5%，所述SiO2粉体占总质量的0.5%～1.5%，余量为ZnO粉体；
将所述靶材装入磁控溅射腔体内，抽真空，设置工作压强为0.2Pa～5Pa，通入惰性气体和氢气的混合气体，混合气体流量为15sccm～25sccm，溅射功率为40W～200W，在衬底上溅射得多元素掺杂氧化锌薄膜。
 有益效果
本发明实施例制备多元素靶材，采用磁控溅射法，溅射得到多元素掺杂氧化锌薄膜，其具有沉积速率高、薄膜附着性好、易控制并能实现大面积沉积等优点。进一步，多元素掺杂能够实现电阻降低，改善光电性能。此外，溅射腔内通过的使用惰性气体和氢气的混合气体作为工作气体，使得低温下就可以获得较低电阻的掺杂氧化锌薄膜。
附图说明
图1是本发明实施例的多元素掺杂氧化锌薄膜的制备方法的流程图；
图2是本发明实施例1的多元素掺杂氧化锌薄膜在紫外-可见波长范围的透射光谱图；
图3是本发明实施例1制备的多元素掺杂氧化锌薄膜在不同使用温度下使用48小时后的电阻变化曲线。
 本发明的实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明作进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
请参阅图1，示出本发明实施例的多元素掺杂氧化锌薄膜的制备方法，其包括如下步骤：
S01：将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体混合，烧结作为靶材，其中，所述Ga2O3粉体占总质量的0.5%～10%，所述Al2O3粉体占总质量的0.5%～5%，所述SiO2粉体占总质量的0.5%～1.5%；
S02：将所述靶材装入磁控溅射腔体内，抽真空，设置工作压强为0.2Pa～5Pa，通入惰性气体和氢气的混合气体，混合气体流量为15 scm～25sccm，溅射功率为40W～200W，在衬底上溅射得多元素掺杂氧化锌薄膜。
步骤S01中，将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体均混合，其中，ZnO为基体。将上述粉体于900℃～1300℃温度下烧结，得到溅射靶材。优选地，所述Ga2O3粉体占总质量的2%～4%，所述Al2O3粉体占总质量的0.8%～1.5%，所述SiO2粉体占总质量的0.6%～1 %。铝和镓能够提高氧化锌的导电性能，硅能够起到稳定导电和稳定化学性能的作用，镓掺杂还可以增加薄膜带隙宽度，扩大透光的波长范围。 步骤S02中，溅射多元素掺杂氧化锌薄膜可以选用石英衬底或者有机柔性衬底。有机柔性衬底包括：聚对苯二甲酸乙二醇酯（PET）、聚碳酸酯（PC）、聚萘二甲酸乙二醇酯（PEN）、聚醚砜（PES）等等。柔性衬底具有柔韧性好，成本低等优点，但是由于其平整性差，熔点低，很多透明导电薄膜的制备工艺不宜选择柔性衬底。衬底通冷却水，使温度控制在100℃以下。衬底使用前用无水乙醇和去离子水超声洗涤，并用高纯氮气吹干。靶材与衬底的距离优选为50mm～90mm。靶材装入溅射腔体内后，抽真空，用机械泵或者分子泵将腔体的真空度抽至1.0×10-3 Pa～1.0×10-5 Pa以上，优选为6.0×10-4 Pa。要得到性能优异的多元素掺杂氧化锌薄膜，工艺条件设置非常重要。溅射腔内的工作气体为惰性气体和氢气的混合气体，其中，氢气摩尔体积百分比为1%～5%，优选地，氢气的摩尔百分比为3%～6%，更优选地，氢气的摩尔体积百分比为5%。气体流量优选为18 sccm～22 sccm，工作压强优选为0.8 Pa～1.2 Pa，溅射功率优选为80 W～120 W。薄膜的厚度一般为150 nm～500 nm。
本发明实施例还提供一种采用所述的多元素掺杂氧化锌薄膜的制备方法制备的多元素掺杂氧化锌薄膜，其在0℃～120℃以下使用，电阻变化率小于15%。
以及上述多元素掺杂氧化锌薄膜在制备半导体光电器件中的应用，主要是在透明加热元件、抗静电、电磁波防护膜、太阳能透明电极的应用。
本发明实施例提供的多元素掺杂氧化锌薄膜的制备方法，采用磁控溅射法，实现了薄膜电阻的最大程度降低，进一步，掺杂使氧化锌具有稳定的导电和化学性能，薄膜带隙宽度增加，同时保持在可见光区的高透过率。而且，溅射过程中采用惰性气体和氢气的混合气体为工作气体，可以在低温下制备得到低电阻的多元素掺杂氧化锌薄膜。
以下结合具体实施例对本发明的具体实现进行详细描述：
实施例1：
将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体均混合，其中，Ga2O3粉体占总质量的1.5%，Al2O3粉体占总质量的2%，SiO2粉体占总质量的1%，ZnO粉体占总质量的95.5%，经过均匀混合后，1250℃高温烧结成Ф50×2 mm的陶瓷靶材，将靶材装入真空腔体内。然后，先后用无水乙醇和去离子水超声清洗PET衬底，并用高纯氮气吹干，放入真空腔体。把靶材和衬底的距离设定为60 mm。用机械泵和分子泵把腔体的真空度抽到6.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为3%（摩尔体积比），混合气体流量为20 sccm，压强调节为1.0 Pa。溅射功率100 W，开始薄膜的沉积。溅射得到多元素掺杂氧化锌薄膜可见光平均透过率大于85%，电阻率为9.3×10-4 Ω•cm。
实施例2：
将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体均混合，其中，Ga2O3粉体占总质量的2.5%，Al2O3粉体占总质量的2%，SiO2粉体占总质量的1%，ZnO粉体占总质量的94.5%，经过均匀混合后，1250℃高温烧结成Ф50×2 mm的陶瓷靶材，将靶材装入真空腔体内。然后，先后用无水乙醇和去离子水超声清洗PET衬底，并用高纯氮气吹干，放入真空腔体。把靶材和衬底的距离设定为60 mm。用机械泵和分子泵把腔体的真空度抽到6.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为5%（摩尔体积比），混合气体流量为20 sccm，压强调节为3.0 Pa。溅射功率120 W，开始薄膜的沉积。溅射得到多元素掺杂氧化锌薄膜可见光平均透过率大于78%，电阻率为8×10-4 Ω•cm。
实施例3：
将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体均混合，其中，Ga2O3粉体占总质量的2%，Al2O3粉体占总质量的2%，SiO2粉体占总质量的1%，ZnO粉体占总质量的95%，经过均匀混合后，1250℃高温烧结成Ф50×2 mm的陶瓷靶材，将靶材装入真空腔体内。然后，先后用无水乙醇和去离子水超声清洗PET衬底，并用高纯氮气吹干，放入真空腔体。把靶材和衬底的距离设定为60 mm。用机械泵和分子泵把腔体的真空度抽到6.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为2%（摩尔体积比），混合气体流量为20 sccm，压强调节为2.0 Pa。溅射功率100 W，开始薄膜的沉积。溅射得到多元素掺杂氧化锌薄膜可见光平均透过率大于80%，电阻率为9.9×10-4 Ω•cm。
实施例4：
将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体均混合，其中，Ga2O3粉体占总质量的5%，Al2O3粉体占总质量的2%，SiO2粉体占总质量的1%，ZnO粉体占总质量的92%，经过均匀混合后，1250℃高温烧结成Ф50×2 mm的陶瓷靶材，将靶材装入真空腔体内。然后，先后用无水乙醇和去离子水超声清洗PET衬底，并用高纯氮气吹干，放入真空腔体。把靶材和衬底的距离设定为60 mm。用机械泵和分子泵把腔体的真空度抽到6.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为1%（摩尔体积比），混合气体流量为20 sccm，压强调节为5.0 Pa。溅射功率90 W，开始薄膜的沉积。溅射得到多元素掺杂氧化锌薄膜可见光平均透过率大于88%，电阻率为2.5×10-3 Ω•cm。
实施例5：
将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体均混合，其中，Ga2O3粉体占总质量的10%，Al2O3粉体占总质量的2%，SiO2粉体占总质量的1%，ZnO粉体占总质量的87%，经过均匀混合后，1250℃高温烧结成Ф50×2 mm的陶瓷靶材，将靶材装入真空腔体内。然后，先后用无水乙醇和去离子水超声清洗PET衬底，并用高纯氮气吹干，放入真空腔体。把靶材和衬底的距离设定为60 mm。用机械泵和分子泵把腔体的真空度抽到6.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为2.5%（摩尔体积比），混合气体流量为20 sccm，压强调节为0.5 Pa。溅射功率80 W，开始薄膜的沉积。溅射得到多元素掺杂氧化锌薄膜可见光平均透过率大于82%，电阻率为3.3×10-3 Ω•cm。
实施例6：
将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体均混合，其中，Ga2O3粉体占总质量的0.5%，Al2O3粉体占总质量的0.5%，SiO2粉体占总质量的0.5%，ZnO粉体占总质量的98.5%，经过均匀混合后，900℃高温烧结成Ф50×2 mm的陶瓷靶材，将靶材装入真空腔体内。然后，先后用无水乙醇和去离子水超声清洗PET衬底，并用高纯氮气吹干，放入真空腔体。把靶材和衬底的距离设定为70 mm。用机械泵和分子泵把腔体的真空度抽到6.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为8%（摩尔体积比），混合气体流量为15 sccm，压强调节为1.0 Pa。溅射功率40 W，开始薄膜的沉积。溅射得到多元素掺杂氧化锌薄膜可见光平均透过率大于72%，电阻率为9.2×10-3Ω•cm。
实施例7：
将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体均混合，其中，Ga2O3粉体占总质量的0.5%，Al2O3粉体占总质量的5%，SiO2粉体占总质量的1.5%，ZnO粉体占总质量的93%，经过均匀混合后，1300℃高温烧结成Ф60×2 mm的陶瓷靶材，将靶材装入真空腔体内。然后，先后用无水乙醇和去离子水超声清洗PC衬底，并用高纯氮气吹干，放入真空腔体。把靶材和衬底的距离设定为90 mm。用机械泵和分子泵把腔体的真空度抽到6.0×10-4 Pa，向真空腔体通入的氩气和氢气的混合气体，其中，氢气含量为10%（摩尔比），混合气体流量为15 sccm，压强调节为1.0 Pa。溅射功率200 W，开始薄膜的沉积。溅射得到多元素掺杂氧化锌薄膜可见光平均透过率大于70%，电阻率为8.2×10-3 Ω•cm。
图2是本发明实施例1制备的PET作为衬底的多元素掺杂氧化锌薄膜在紫外-可见光波长范围的透射光谱，从图中可以得出，其可见光透光率大于85%。图3是实施例1制备的多元素掺杂氧化锌薄膜在不同使用温度下使用48小时的电阻变化曲线。电阻变化率是多元素掺杂氧化锌薄膜在图示温度下加热48小时后，由四探针测试得到的新方块电阻R1，该电阻值与原电阻值R0之差，再除以原电阻R0得到；即电阻变化率R% = (R1-R0) / R0。图中显示出，在120℃下使用48小时电阻变化率小于15%，已经达到了工业化生产的性能标准。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种多元素掺杂氧化锌薄膜的制备方法，其特征在于，所述方法包括如下步骤：
    将Ga2O3粉体、Al2O3粉体、SiO2粉体和ZnO粉体混合，烧结作为靶材，其中，所述Ga2O3粉体占总质量的0.5%～10%，所述Al2O3粉体占总质量的0.5%～5%，所述SiO2粉体占总质量的0.5%～1.5%，余量为ZnO粉体；
    将所述靶材装入磁控溅射腔体内，抽真空，设置工作压强为0.2Pa～5Pa，通入惰性气体和氢气的混合气体，混合气体流量为15sccm～25sccm，溅射功率为40W～200W，在衬底上溅射得多元素掺杂氧化锌薄膜。
  2. 如权利要求1所述的多元素掺杂氧化锌薄膜的制备方法，其特征在于，所述Ga2O3粉体占总质量的2%～4%，所述Al2O3粉体占总质量的0.8%～1.5%，所述SiO2粉体占总质量的0.6%～1 %，余量为ZnO粉体。
  3. 如权利要求1所述的多元素掺杂氧化锌薄膜的制备方法，其特征在于，所述混合气体流量为18sccm ～22sccm，所述腔体的工作压强为0.8Pa～1.2Pa。
  4. 如权利要求1所述的多元素掺杂氧化锌薄膜的制备方法，其特征在于，所述混合气体中氢气的摩尔体积百分含量为1%～10%。
  5. 如权利要求1所述的多元素掺杂氧化锌薄膜的制备方法，其特征在于，所述混合气体中氢气的摩尔体积百分含量为3%～6%。
  6. 如权利要求1所述的多元素掺杂氧化锌薄膜的制备方法，其特征在于，所述衬底为有机柔性衬底。
  7. 如权利要求1所述的多元素掺杂氧化锌薄膜的制备方法，其特征在于，所述衬底的温度控制在0℃ ～100℃。
  8. 如权利要求1～7任一所述的多元素掺杂氧化锌薄膜的制备方法制得的多元素掺杂氧化锌薄膜。
  9. 如权利要求8所述的多元素掺杂氧化锌薄膜，其特征在于，所述多元素掺杂氧化锌薄膜在0℃～120℃使用48小时后电阻变化率小于15%。
  10. 如权利要求8或9所述的多元素掺杂氧化锌薄膜在半导体光电器件中的应用。
PCT/CN2011/072144 2011-03-25 2011-03-25 多元素掺杂氧化锌薄膜及其制备方法和应用 WO2012129757A1 (zh)

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