PatViewer专利搜索
中国 发明 无效

Ag/ZnO/Mg光电透明导电薄膜的沉积方法 【EN】Depositing method for Ag/ZnO/Mg photoelectric transparent conducting thin film

申请(专利)号:CN201611094524.7国省代码:广东 44
申请(专利权)人:【中文】梁结平【EN】Liang Jieping
温馨提示:Ctrl+D 请注意收藏,详细著录项请登录检索查看。 Please note the collection. For details, please search the home page.

摘要:
【中文】本发明涉及一种Ag/ZnO/Mg光电透明导电薄膜的沉积方法,属透明导电材料领域。本发明一种按照以下步骤进行:(1)将基片用丙酮、乙醇以及去离子水用超声波依次清洗后,用氮气吹干送入反应室;2)磁控溅射Mg膜的沉积;(3)有机物化学气相沉积制备中间层ZnO薄膜:(4)磁控溅射Ag膜的沉积:(5)对Ag/ZnO/Mg的多层结构的透明导电薄膜进行高温退火,退火温度为200~600℃,退火时间为20min,得到Ag、Mg共同掺杂的ZnO光电透明导电薄膜。本发明制备工艺简单,沉积过程易于控制。本发明制备的透明导电薄膜均匀性好,光电性能优异,电阻率可低至7.0×10 【EN】Paragraph:The invention relates to a depositing method for an Ag/ZnO/Mg photoelectric transparent conducting thin film, and belongs to the field of transparent conducting materials. The depositing method is conducted according to the following steps that (1) a substrate is subjected to ultrasonic cleaning sequentially with acetone, ethyl alcohol and deionized water, then dried with nitrogen and put into a reaction chamber; (2) deposition of a magnetron sputtering Mg film is conducted; (3) a middle layer ZnO thin film is prepared through organic matter chemical vapor deposition; (4) deposition of a magnetron sputtering Ag film is conducted; and (5) the transparent conducting thin film of the Ag/ZnO/Mg multi-layer structure is subjected to high-temperature annealing, the annealing temperature is 200-600 DEG C, the annealing time is 20 min, and the ZnO photoelectric transparent conducting thin film jointly doped with Ag and Mg is obtained. The preparation process is simple, and the depositing process is easy to control. The prepared transparent conducting thin film is good in uniformity and excellent in photoelectric performance, the electrical resistivity can be as low as 7.0*10<-4> ohm.cm, and the light transmittance can reach 85% or above. The transparent conducting thin film can be used for manufacturing transparent electrodes of photoelectric devices such as solar cells, light emitting diodes, LCDs and mobile phones.Image:201611094524.GIF

主权项:
【中文】1.一种Ag/ZnO/Mg光电透明导电薄膜的沉积方法,其特征在于按照以下步骤进行: (1)将基片用丙酮、乙醇以及去离子水用超声波依次清洗后,用氮气吹干送入反应室; (2)磁控溅射Mg膜的沉积:将沉积室本底抽到9.5×10Pa之后,通入氩气,在基片衬底上射频溅射Mg靶材,沉积制备厚度为20~60nmMg薄膜; (3)有机物化学气相沉积制备中间层ZnO薄膜:将沉积反应室真空抽至7.5×10Pa后,将沉积上Mg膜的基片加热至50~450℃,向反应室内同时通入氩气携带的Zn(CHCH)和O,Zn(CHCH)和O量由质量流量计控制流量比为(2~4):(200~400),控制气体总压强为0.9~2.1Pa;在电子回旋共振频率为750W,反应25~45min,得到450~650nm的ZnO薄膜; (4)磁控溅射Ag膜的沉积:将沉积室本底抽到8.5×10Pa之后,通入氩气,在ZnO/Mg基片上射频溅射Ag靶材,沉积制备厚度为15~45nm的Ag薄膜; (5)对Ag/ZnO/Mg的多层结构的透明导电薄膜进行高温退火,退火温度为200~600℃,退火时间为20min,得到Ag、Mg共同掺杂的ZnO光电透明导电薄膜。 【EN】1. a kind of deposition process of Ag/ZnO/Mg photoelectricity transparent conductive film, it is characterised in that follow the steps below: (1) after successively cleaning substrate acetone, ethanol and deionized water ultrasonic wave, with nitrogen feeding reative cell is dried up; (2) deposition of magnetron sputtering Mg films:Settling chamber's background is extracted into 9.5 × 10After Pa, argon gas is passed through, in base substrate Upper radio-frequency sputtering Mg targets, deposition prepares thickness for 20~60nmMg films; (3) organic chemical vapor deposition prepares intermediate layer ZnO film:Cvd reactive chamber vacuum is evacuated into 7.5 × 10After Pa, By the substrate heating of the upper Mg films of deposition to 50~450 DEG C, to the indoor Zn (CH for being passed through argon gas carrying simultaneously of reactionCH)And O, Zn(CHCH)And OAmount controls flow-rate ratio for (2~4) by mass flowmenter:(200~400), control gas total pressure for 0.9 ~2.1Pa;It is 750W in electron cyclotron resonance frequency, reacts 25~45min, obtains the ZnO film of 450~650nm; (4) deposition of magnetron sputtering Ag films:Settling chamber's background is extracted into 8.5 × 10After Pa, argon gas is passed through, in ZnO/Mg bases Radio-frequency sputtering Ag targets on piece, deposition prepares the Ag films that thickness is 15~45nm; (5) high annealing is carried out to the transparent conductive film of the sandwich construction of Ag/ZnO/Mg, annealing temperature is 200~600 DEG C, Annealing time is 20min, obtains the ZnO photoelectricity transparent conductive films of Ag, Mg co-doped.


说明书

【中文】

Ag/ZnO/Mg光电透明导电薄膜的沉积方法

技术领域

本发明属透明导电材料领域,特别涉及一种Ag/ZnO/Mg光电透明导电薄膜的沉积方法。

背景技术

随着社会发展和科学技术的突飞猛进,人类对功能材料的需求日益增加,新型功能材料已成为新技术和新兴工业发展的关键。随着太阳能、平板显示和半导体照明等产业的发展,一种新的功能材料——透明导电材料随之产生、发展起来。

透明导电膜玻璃即透明导电氧化物镀膜玻璃,是在平板玻璃表面通过物理或者化学镀膜的方法均匀镀上一层TCO薄膜。目前应用中的TCO材料主要为三类,ITO-In2O3基薄膜(Sn掺杂)、FTO-SnO2基薄膜(F掺杂)和AZO-ZnO基薄膜(Al掺杂)等。

ITO-In2O3的晶体结构为体心立方铁锰矿结构,禁带宽度约3.5eV,因而在可见光范围透明,Tavg〉90%。ITO最低电阻率可达10-5Ω.cm量级。ITO是目前最成熟、应用最广泛的TCO,目前除了TFT-LCD面板几乎都使用ITO外,替代传统的太阳能电池的铝背电极而形成新型的太阳能电池的透明导电电极和薄膜太阳能电池也都使用。不过由于ITO须使用稀有金属铟(中国铟保有储量1.3万吨,约占全球2/3),从而导致生产成本很高。随着TFT-LCD面板市场持续扩增和太阳能电池的进一步发展,全球铟消费量的83%用于ITO,从而也引发了铟矿在未来将逐渐耗尽的问题。而且铟材料有毒,在制备和应用过程中对人体有害。另外铟和锡的原子量较大,成膜过程中容易渗入到衬底内部,毒化衬底材料,尤其在液晶显示器件中污染现象严重。对于太阳能行业来说,TCO玻璃必须具备提高光散射的能力,而ITO镀膜很难做到这一点,并且激光刻蚀性能较差、ITO在等离子体中并不够稳定(一般硅薄膜太阳能电池需要在等离子体条件下制作),因此目前ITO已非光伏电池主流的电极材料。总之,寻找合适的替代产品势在必行。

FTO-SnO2具有正四面体的金红石结构,禁带宽度为3.6eV,通过掺杂氟得到FTO薄膜,可以进一步增强导电性能。FTO与ITO相比具有热稳定性高、耐腐蚀、硬度高等优势,并且在等离子体中也具有很好的稳定性,从而成为目前商业化应用的光伏TCO材料。但是,高结晶质量FTO薄膜制备比较困难,对制备工艺要求高,由于薄膜内部缺陷的存在而使其透光率与电导率低于ITO薄膜;同时由于需要氟元素(剧毒)掺杂因而工艺过程存在一定的污染。此外,由于FTO薄膜硬度高因而比较难于刻蚀。

ZnO基薄膜。ZnO属于N型Ⅱ-Ⅵ族半导体材料,其晶体结构为六方纤锌矿结构禁带宽度约3.4eV,透光率可达90%以上。同时ZnO在不掺杂的情况下由于本征氧空位缺陷的存在也具有较高的电导率,通过III族元素(Al、Ga、B)掺杂可以进一步提高导电性。ZnO用于TCO薄膜具有原料丰富、成本低廉、制备工艺简单、无毒、不污染环境等显著的优势。而且,ZnO能够在氢等离子体中稳定性要优于ITO薄膜,具有可与ITO薄膜相比拟的光电特性的同时又易于刻蚀。另外ZnO可高效透射ITO难以透射的短波长光线,因而无论是在太阳能电池还是平板显示上,ZnO都是替代ITO与FTO的有力竞争者。

发明内容

针对现有材料存在的不足,本发明通过在基片衬底上依次进行磁控溅射Mg薄膜,然后利用有机物化学气相沉积制备中间层ZnO薄膜,最后磁控溅射Ag薄膜,之后对实验薄膜样品进行高温退火处理,得到Ag/ZnO/Mg结构的透明导电薄膜。

本发明一种Ag/ZnO/Mg光电透明导电薄膜的沉积方法,其特征在于按照以下步骤进行:

(1)将基片用丙酮、乙醇以及去离子水用超声波依次清洗后,用氮气吹干送入反应室;

(2)磁控溅射Mg膜的沉积:将沉积室本底抽到9.5×10-4Pa之后,通入氩气,在基片衬底上射频溅射Mg靶材,沉积制备厚度为20~60nmMg薄膜;

(3)有机物化学气相沉积制备中间层ZnO薄膜:将沉积反应室真空抽至7.5×10-4Pa后,将沉积上Mg膜的基片加热至50~450℃,向反应室内同时通入氩气携带的Zn(CH2CH3)2和O2,Zn(CH2CH3)2和O2量由质量流量计控制流量比为(2~4):(200~400),控制气体总压强为0.9~2.1Pa;在电子回旋共振频率为750W,反应25~45min,得到450~650nm的ZnO薄膜;

(4)磁控溅射Ag膜的沉积:将沉积室本底抽到8.5×10-4Pa之后,通入氩气,在ZnO/Mg基片上射频溅射Ag靶材,沉积制备厚度为15~45nm的Ag薄膜;

(5)对Ag/ZnO/Mg的多层结构的透明导电薄膜进行高温退火,退火温度为200~600℃,退火时间为20min,得到Ag、Mg共同掺杂的ZnO光电透明导电薄膜。

作为优选,所述基片为普通康宁玻璃、蓝宝石、石英、太阳能电池片、硅片或有机聚合物。

作为优选,所述步骤(2)中磁控溅射Mg膜的沉积条件具体为:对基片衬底进行加热至150℃并调整氩气气体流量使气压达到6Pa,溅射功率为150W,溅射时间为2~6min,使得Mg薄膜厚度为20~60nm。

作为优选,所述步骤(4)磁控溅射Ag膜的沉积条件具体为:ZnO/Mg基片进行加热至200℃,并调整氩气气体流量使气压达到9Pa,溅射功率为150W,溅射时间为1~4min,使得Ag膜的厚度是15~45nm。

本发明采用等离子增强电子回旋共振有机物化学气相沉积技术与磁控溅射技术相结合的方式,利用ZnO良好的光电性能和Ag、Mg的低电阻率,形成Ag/ZnO/Mg的结构,在经过高温退火处理。由于Ag、Mg的掺入,载流子浓度增加,薄膜的导电性能得到了很大的提高,同时可保持透光率达到85%以上。

本发明制备工艺简单,沉积过程易于控制。本发明制备的透明导电薄膜均匀性好,光电性能优异,电阻率可低至7.0×10-4Ω·cm,而其透光率可达85%以上。可用于制造太阳能电池、发光二极管、LCD以及手机等光电器件的透明电极。

附图说明

图1为本发明方法得到的Ag/ZnO/Mg透明导电薄膜示意图。

图中1为基片,2为Mg薄膜,3为中间层ZnO透明导电薄膜,4为Ag薄膜。

具体实施方式

下面通过实施例对本发明的内容进一步说明,本发明的保护范围不限于下述的实施例。

实施例1

将基片用丙酮、乙醇以及去离子水用超声波依次清洗后,用氮气吹干送入反应室。

将磁控溅射的本底真空抽至9.5×10-4Pa后,对基片衬底进行加热至150℃并调整气体流量使气压达到6Pa,溅射功率为150W,溅射时间为2min,Mg薄膜厚度为20nm。

然后,利用等离子增强电子回旋共振化学气相沉积的方法沉积制备ZnO薄膜,真空抽至7.5×10-4Pa后,将基片加热至150℃,向反应室内同时通入氩气携带的Zn(CH2CH3)2和O2后,Zn(CH2CH3)2和O2量由质量流量计控制流量比为2sccm:200sccm,控制气体总压强为1.5Pa;在电子回旋共振频率为750W,反应25min,得到450nm的ZnO薄膜。

然后将所制备的薄膜经过清洗处理后其放入磁控溅射室,进行Ag薄膜的溅射,对基片衬底进行加热至200℃并调整气体流量使气压达到9Pa,溅射功率为150W,溅射时间为1min的Ag薄膜,其薄膜厚度为15nm。

最后在高温的情形下对该结构薄膜进行高温退火处理,其退火温度为200℃,退火时间为20min。得到的Ag/ZnO/Mg透明导电薄膜示意图如图1所示,1为基片,2为Mg薄膜,3为中间层ZnO透明导电薄膜,4为Ag薄膜。

对Ag/ZnO/Mg光电透明导电薄膜的电学性能进行了测试,其与普通磁控溅射沉积制备ZnO的电学性能对比如表1所示,由表1可以看出Ag/ZnO/Mg光电透明导电薄膜与普通磁控溅射沉积制备ZnO薄膜相比,电阻率明显降低,迁移率和载流子浓度明显增加。

表1 Ag/ZnO/Mg光电透明导电薄膜的沉积方法与普通磁控溅射沉积制备ZnO的电学性能对比

实施例2

将基片用丙酮、乙醇以及去离子水用超声波依次清洗后,用氮气吹干送入反应室。

将磁控溅射的本底真空抽至9.5×10-4Pa后,对基片衬底进行加热至150℃并调整气体流量使气压达到6Pa,溅射功率为150W,溅射时间为6min,Mg薄膜厚度为60nm。

然后,利用等离子增强电子回旋共振化学气相沉积的方法沉积制备ZnO薄膜,真空抽至7.5×10-4Pa后,将基片加热至300℃,向反应室内同时通入氩气携带的Zn(CH2CH3)2和O2后,Zn(CH2CH3)2和O2量由质量流量计控制流量比为4sccm:200sccm,控制气体总压强为1.5Pa;在电子回旋共振频率为750W,反应45min,得到650nm的ZnO薄膜。

然后将所制备的薄膜经过清洗处理后其放入磁控溅射室,进行Ag薄膜的溅射,对基片衬底进行加热至200℃并调整气体流量使气压达到9Pa,溅射功率为150W,溅射时间为4min的Ag薄膜,其薄膜厚度为45nm。

最后在高温的情形下对该结构薄膜进行高温退火处理,其退火温度为600℃,退火时间为20min,以得到的Ag/ZnO/Mg透明导电薄膜,对Ag/ZnO/Mg光电透明导电薄膜的电学性能进行了测试,其与普通磁控溅射沉积制备ZnO的电学性能对比如表2所示,由表2可以看出Ag/ZnO/Mg光电透明导电薄膜与普通磁控溅射沉积制备ZnO薄膜相比,电阻率明显降低,迁移率和载流子浓度明显增加。

表2Ag/ZnO/Mg光电透明导电薄膜的沉积方法与普通磁控溅射沉积制备ZnO的电学性能对比

以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。

【EN】

The deposition process of Ag/ZnO/Mg photoelectricity transparent conductive films

Technical field

The invention belongs to transparent conductive material field, more particularly to a kind of deposition of Ag/ZnO/Mg photoelectricity transparent conductive film

Method.

Background technology

As social development is advanced by leaps and bounds with scientific and technical, the mankind increasingly increase the demand of functional material, new work(

Energy material has become the key of new technology and infant industry's development.With industries such as solar energy, FPD and semiconductor lightings

Development, therewith Emergence and Development gets up a kind of new functional material --- transparent conductive material.

Transparent conducting film glass is transparent conductive oxide coated glass, is by physics or change in surface of plate glass

The method for learning plated film uniformly plates last layer TCO thin film.At present the TCO materials in application are mainly three classes, ITO-In2O3 base films

(Sn doping), FTO-SnO2 base films (F doping) and AZO-ZnO base films (Al doping) etc..

The crystal structure of ITO-In2O3 is body-centered cubic Ferromanganese Ore structure, energy gap about 3.5eV, thus in visible ray

Scope is transparent, Tavg > 90%.ITO lowest resistivities are up to 10-5 Ω .cm magnitudes.ITO is most ripe, most widely used at present

TCO, at present except TFT-LCD panels are nearly all using in addition to ITO, substitute the aluminum back electrode of traditional solar cell and formed

The transparency conductive electrode and thin-film solar cells of new solar cell is also all used.But due to ITO must use it is rare

(2/3) 1.3 ten thousand tons of Chinese indium reserves accounts for the whole world, so as to cause production cost very high to indium metal.With TFT-LCD faces

Plate market persistently expands the further development with solar cell, and the 83% of global indium consumption figure is used for ITO, so as to also cause

The problem that indium ore deposit will be gradually exhausted in future.It is harmful with application process preparing and phosphide material is poisonous.Other indium

It is larger with the atomic weight of tin, substrate interior is easily infiltrated into film forming procedure, poison backing material, especially in liquid crystal display device

Middle contamination phenomenon is serious.For solar energy industry, TCO glass must possess the ability for improving light scattering, and ITO plated films are very

Difficulty accomplishes this point, and laser ablation poor-performing, ITO in the plasma and are not sufficiently stable (general silicon film solar

Battery needs to make under plasma conditions), therefore the at present electrode material of ITO non-photovoltaic cell main flows.In a word, find

Suitable substitute products are imperative.

FTO-SnO2 has the rutile structure of positive tetrahedron, and energy gap is 3.6eV, obtains FTO by the fluorine that adulterates thin

Film, can further enhance electric conductivity.FTO compared with ITO with heat endurance is high, corrosion-resistant, the advantage such as hardness is high, and

Also there is in the plasma good stability, so as to become the photovoltaic TCO materials of current commercial applications.But, Gao Jie

Crystalloid amount FTO film preparation is relatively difficult, and preparation technology is had high demands, and due to the presence of film internal flaw its light transmittance is made

Ito thin film is less than with electrical conductivity;Simultaneously because need fluorine element (severe toxicity) adulterate thus there is certain pollution in technical process.This

Outward, due to FTO film hardness is high thus be relatively difficult to etching.

Zno-based film.ZnO belongs to the race's semi-conducting material of N-type II-VI, and its crystal structure is hexagonal wurtzite structure forbidden band

Width about 3.4eV, light transmittance is up to more than 90%.While ZnO depositing due to intrinsic Lacking oxygen defect in the case of plain

Also there is higher electrical conductivity, electric conductivity can be further being improved by group-III element (Al, Ga, B) doping.ZnO is used for

TCO thin film has the significant advantage such as abundant raw material, with low cost, preparation process is simple, nontoxic, free from environmental pollution.And,

ZnO stability can be better than ito thin film in hydrogen plasma, with can be comparable with ito thin film photoelectric characteristic it is same

When be easy to again etching.In addition ZnO can high efficiency transmission ITO be difficult to the short wavelength light that transmits, thus either in solar cell

Or in FPD, ZnO is the contenders for substituting ITO and FTO.

The content of the invention

It is of the invention by carrying out magnetron sputtering Mg films successively in base substrate for the deficiency that current material is present,

Then intermediate layer ZnO film, last magnetron sputtering Ag films, afterwards to experimental thin films are prepared using organic chemical vapor deposition

Sample carries out the high temperature anneal, obtains the transparent conductive film of Ag/ZnO/Mg structures.

A kind of deposition process of Ag/ZnO/Mg photoelectricity transparent conductive film of the present invention, it is characterised in that according to following steps

Carry out:

(1) after successively cleaning substrate acetone, ethanol and deionized water ultrasonic wave, with nitrogen feeding reaction is dried up

Room;

(2) deposition of magnetron sputtering Mg films:Settling chamber's background is extracted into 9.5 × 10-4After Pa, argon gas is passed through, in substrate

Radio-frequency sputtering Mg targets on substrate, deposition prepares thickness for 20~60nmMg films;

(3) organic chemical vapor deposition prepares intermediate layer ZnO film:Cvd reactive chamber vacuum is evacuated into 7.5 × 10-4Pa

Afterwards, by the substrate heating of the upper Mg films of deposition to 50~450 DEG C, to the indoor Zn (CH for being passed through argon gas carrying simultaneously of reaction2CH3)2With

O2, Zn (CH2CH3)2And O2Amount controls flow-rate ratio for (2~4) by mass flowmenter:(200~400), controlling gas total pressure is

0.9~2.1Pa;It is 750W in electron cyclotron resonance frequency, reacts 25~45min, obtains the ZnO film of 450~650nm;

(4) deposition of magnetron sputtering Ag films:Settling chamber's background is extracted into 8.5 × 10-4After Pa, argon gas is passed through, in ZnO/

Radio-frequency sputtering Ag targets on Mg substrates, deposition prepares the Ag films that thickness is 15~45nm;

(5) high annealing is carried out to the transparent conductive film of the sandwich construction of Ag/ZnO/Mg, annealing temperature is 200~600

DEG C, annealing time is 20min, obtains the ZnO photoelectricity transparent conductive films of Ag, Mg co-doped.

Preferably, the substrate is common corning glass, sapphire, quartz, solar battery sheet, silicon chip or organic poly-

Compound.

Preferably, the sedimentary condition of magnetron sputtering Mg films is specially in the step (2):Base substrate is heated

To 150 DEG C and adjusting argon gas flow makes air pressure reach 6Pa, sputtering power is 150W, and sputtering time is 2~6min so that

Mg film thicknesses are 20~60nm.

Preferably, the sedimentary condition of step (4) the magnetron sputtering Ag films is specially:ZnO/Mg substrates are heated to

200 DEG C, and adjusting argon gas flow makes air pressure reach 9Pa, sputtering power is 150W, and sputtering time is 1~4min so that Ag

The thickness of film is 15~45nm.

The present invention strengthens electron cyclotron resonace organic chemical vapor deposition technology and magnetron sputtering technique using plasma

The mode for combining, using the low-resistivity of ZnO good photoelectric properties and Ag, Mg, forms the structure of Ag/ZnO/Mg, in Jing

Cross the high temperature anneal.Because the incorporation of Ag, Mg, carrier concentration increase, the electric conductivity of film is greatly improved,

Simultaneously light transmittance can be kept to reach more than 85%.

Preparation process is simple of the present invention, deposition process is easily controllable.Transparent conductive film uniformity prepared by the present invention is good,

Photoelectric properties are excellent, and resistivity can as little as 7.0 × 10-4Ω cm, and its light transmittance is up to more than 85%.Can be used to manufacture the sun

The transparency electrode of the photoelectric devices such as energy battery, light emitting diode, LCD and mobile phone.

Description of the drawings

The Ag/ZnO/Mg transparent conductive film schematic diagrames that Fig. 1 is obtained for the inventive method.

1 is substrate in figure, and 2 is Mg films, and 3 is intermediate layer ZnO transparent conductive thin film, and 4 is Ag films.

Specific embodiment

Present disclosure is further illustrated below by embodiment, protection scope of the present invention is not limited to following realities

Apply example.

Embodiment 1

After substrate acetone, ethanol and deionized water ultrasonic wave are cleaned successively, with nitrogen feeding reative cell is dried up.

The base vacuum of magnetron sputtering is evacuated into 9.5 × 10-4After Pa, base substrate is carried out to be heated to 150 DEG C and adjust

Gas flow makes air pressure reach 6Pa, and sputtering power is 150W, and sputtering time is 2min, and Mg film thicknesses are 20nm.

Then, the method deposition for strengthening electron cyclotron resonance chemical vapor deposition using plasma prepares ZnO film, vacuum

It is evacuated to 7.5 × 10-4After Pa, by substrate heating to 150 DEG C, to the indoor Zn (CH for being passed through argon gas carrying simultaneously of reaction2CH3)2And O2

Afterwards, Zn (CH2CH3)2And O2Amount controls flow-rate ratio for 2sccm by mass flowmenter:200sccm, controlling gas total pressure is

1.5Pa;It is 750W in electron cyclotron resonance frequency, reacts 25min, obtains the ZnO film of 450nm.

Then by prepared film after cleaning treatment its be put into magnetron sputtering chamber, carry out the sputtering of Ag films, it is right

Base substrate carries out being heated to 200 DEG C and adjusting gas flow makes air pressure reach 9Pa, and sputtering power is 150W, and sputtering time is

The Ag films of 1min, its film thickness is 15nm.

Finally the high temperature anneal is carried out to the structural membrane in the case of high temperature, its annealing temperature is 200 DEG C, annealing

Time is 20min.As shown in figure 1,1 is substrate, 2 is Mg films, and 3 are for the Ag/ZnO/Mg transparent conductive films schematic diagram that obtains

Intermediate layer ZnO transparent conductive thin film, 4 is Ag films.

The electric property of Ag/ZnO/Mg photoelectricity transparent conductive films is tested, itself and common magnetron sputtering sedimentation

The electric property contrast for preparing ZnO is as shown in table 1, as can be seen from Table 1 Ag/ZnO/Mg photoelectricity transparent conductive film and common magnetic

Control sputtering sedimentation prepares ZnO film and compares, and resistivity is substantially reduced, and mobility and carrier concentration substantially increase.

The deposition process of the Ag/ZnO/Mg photoelectricity transparent conductive films of table 1 prepares the electricity of ZnO with common magnetron sputtering sedimentation

Learn performance comparison

Embodiment 2

After substrate acetone, ethanol and deionized water ultrasonic wave are cleaned successively, with nitrogen feeding reative cell is dried up.

The base vacuum of magnetron sputtering is evacuated into 9.5 × 10-4After Pa, base substrate is carried out to be heated to 150 DEG C and adjust

Gas flow makes air pressure reach 6Pa, and sputtering power is 150W, and sputtering time is 6min, and Mg film thicknesses are 60nm.

Then, the method deposition for strengthening electron cyclotron resonance chemical vapor deposition using plasma prepares ZnO film, vacuum

It is evacuated to 7.5 × 10-4After Pa, by substrate heating to 300 DEG C, to the indoor Zn (CH for being passed through argon gas carrying simultaneously of reaction2CH3)2And O2

Afterwards, Zn (CH2CH3)2And O2Amount controls flow-rate ratio for 4sccm by mass flowmenter:200sccm, controlling gas total pressure is

1.5Pa;It is 750W in electron cyclotron resonance frequency, reacts 45min, obtains the ZnO film of 650nm.

Then by prepared film after cleaning treatment its be put into magnetron sputtering chamber, carry out the sputtering of Ag films, it is right

Base substrate carries out being heated to 200 DEG C and adjusting gas flow makes air pressure reach 9Pa, and sputtering power is 150W, and sputtering time is

The Ag films of 4min, its film thickness is 45nm.

Finally the high temperature anneal is carried out to the structural membrane in the case of high temperature, its annealing temperature is 600 DEG C, annealing

Time is 20min, with the Ag/ZnO/Mg transparent conductive films for obtaining, the electrical property to Ag/ZnO/Mg photoelectricity transparent conductive films

Can be tested, the electric property contrast that it prepares ZnO with common magnetron sputtering sedimentation is as shown in table 2, as can be seen from Table 2

Compared with common magnetron sputtering sedimentation prepares ZnO film, resistivity is substantially reduced Ag/ZnO/Mg photoelectricity transparent conductive film, is moved

Shifting rate and carrier concentration substantially increase.

The deposition process of table 2Ag/ZnO/Mg photoelectricity transparent conductive films prepares the electricity of ZnO with common magnetron sputtering sedimentation

Performance comparison

The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art

For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as

Protection scope of the present invention.

图1
PatViewer知识产权搜索   专利、商标、地理标志、集成电路
©2018 IPPH.cn  主办单位:国家知识产权局知识产权出版社  咨询热线:01082000860-8588
浏览器:火狐、谷歌、opera、ie9及以上等  京ICP备09007110号 京公网安备 11010802026659号 开放平台