CN101528987A - 有效的镓薄膜电镀方法和化学组合物 - Google Patents
有效的镓薄膜电镀方法和化学组合物 Download PDFInfo
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- CN101528987A CN101528987A CNA2007800391728A CN200780039172A CN101528987A CN 101528987 A CN101528987 A CN 101528987A CN A2007800391728 A CNA2007800391728 A CN A2007800391728A CN 200780039172 A CN200780039172 A CN 200780039172A CN 101528987 A CN101528987 A CN 101528987A
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- solution
- citrate
- complexing agent
- obtains
- gallium
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- 229910052700 potassium Inorganic materials 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- 229960004799 tryptophan Drugs 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
Abstract
本发明涉及以高镀覆效率和可再现性沉积均匀、无缺陷和平滑的Ga膜的镓(Ga)电镀方法和化学组合物。这些层可用于制造电子器件如薄膜太阳能电池。在一个实施方案中,本发明提供了施加在导体上的溶液,该溶液包含Ga盐、络合剂、溶剂,并在将该溶液电沉积到导体上时形成具有亚微米厚度的Ga膜。该溶液还可以包含Cu盐和In盐之一或两者。
Description
相关申请的交叉引用:
本申请要求2007年9月27日提交的名为“Efficient GalliumThin Film Electroplating Methods and Chemistries”的美国专利申请no.11/535,927的优先权,通过引用将其并入本文。
发明领域:
[0001]本发明涉及以高的镀覆效率和可再现性来沉积均匀、无缺陷和平滑的Ga膜的镓(Ga)电镀方法和化学组合物(chemistry)。这样的层可用于制造电子器件如薄膜太阳能电池。
背景:
[0002]镓是半导体和电子工业中使用的元素。镓通常作为副产物从含铝酸钠的拜耳(Bayer)工艺液回收(参见例如美国专利2,793,179和美国专利2,582,377)。尽管电沉积是用于从碱性或酸性溶液中回收块体Ga(参见例如美国专利3,904,497)或用于纯化块体Ga的常见方法,但在以受控均匀性、形貌和厚度沉积薄膜的情况下,这种材料尚未大量应用。因此,只开发和报道了少数在用于电子应用的衬底上沉积Ga薄层的电镀浴化学组合物和方法。例如,S.Sundararajan和T.Bhat(J.Less Common Metals,第11卷,第360页,1966)评价了pH值在0至5之间不等的氯化镓溶液用于电镀Ga膜。其他研究人员研究了从包含水和/或甘油的高pH值溶液中沉积出Ga。例如,Bockris和Enyo使用含氯化镓和NaOH的碱性电解液(J.Electrochemical Society,第109卷,第48页,1962),而P.Andreoli等人(Journal of Electroanalytical Chemistry,第385卷,第265页,1995)研究了包含KOH和氯化镓的电解液。
[0003]据报道,上述现有技术方法和镀覆浴都实现了Ga膜沉积。但是,仍存在与现有技术的电化学沉积法相关的一些常见问题。这些问题包括,由过度氢生成引起的低阴极沉积效率、部分地由差的阴极效率引起的该方法的不良可再现性、和沉积膜的不良品质例如其高表面粗糙度和差的形貌。这些问题对于块体Ga电镀或对于为了研究科学论题如沉积机制而沉积的Ga膜可能不重要。差的膜形貌或不足的厚度控制对于Ga层的电惰性用途(如其作为润滑涂层等的用途)可能也不重要。但是,对于Ga膜在电子器件(如太阳能电池)的活性(active)部分的形成中起到一定作用的某些新兴电子用途,Ga膜的性质变得重要。
[0004]采用在酸性或碱性pH值下工作的简单电解液的现有技术的Ga电镀技术出于各种原因不适合上述电子用途,所述原因包括,它们造成差的镀覆效率和具有粗糙形貌(表面粗糙度通常大于膜厚度的大约20%)的膜。镓是难以在无过量氢生成的情况下在阴极上沉积的金属,因为Ga镀覆电势高。阴极上的氢生成造成沉积效率低于100%,因为部分沉积电流被用于形成氢气而非在衬底或阴极上形成Ga膜。由于微小的氢气泡附着于沉积膜表面、遮蔽它们下方的微区域且因此阻碍在该微区域上的沉积,因此氢生成和析出也造成沉积膜上的不良形貌和微缺陷。这造成膜叠层中的具有少于最佳量Ga的微区域。差的镀覆效率固有地降低电沉积法的可再现性,因为氢生成现象本身强烈地取决于许多因素,包括电解液中的杂质、沉积电流密度、衬底表面的形貌或化学组合物的小变化、温度、质量传递等。由于这些因素中的至少一种可能随批次(run)而变,氢生成速率也可能改变,以致改变沉积效率。
[0005]从低pH值水性电解液或溶液中电沉积Ga可能遭受由这样的电解液中大浓度的H+物质的存在而引起的低阴极效率。因此,可预计在较高pH值下氢气生成减少。但是,随着溶液中的pH值升高,Ga形成可能沉淀的氧化物和氢氧化物,如文献中报道的那样。只有在极碱性pH值下,这些氧化物/氢氧化物才作为可溶Ga物质而溶解。因此,如在浴配制剂中使用高浓度KOH和NaOH的现有技术中那样,在含Ga盐的pH>14的浴中电沉积Ga变为可能。但是,碱性物质的高浓度造成设备以及阴极材料本身的腐蚀问题。在Ga开始沉淀之前可以按酸性Ga盐(GaCl3,Ga(NO3)3等)形式溶解在这样的溶液中的Ga量也有限。因此,需要再次通过进一步添加碱性物质如NaOH和KOH来调节pH。如上指出,难以处理包含大摩尔量苛性物质(caustics)的溶液且它们还具有高粘度。高粘度使得在阴极上形成的氢气泡更附着到阴极上,以致极难通过搅拌或其它质量传递方式除去它们。如上所述,阴极表面上的这些气泡提高了沉积的Ga层的缺陷性。
[0006]从前文的论述可以看出,需要开发可以提供可用于电子用途(如加工薄膜太阳能电池)中的高品质电沉积Ga层的新型电镀化学组合物和方法。
发明概述
[0007]本发明涉及以高镀覆效率和可再现性沉积均匀、无缺陷且平滑的Ga膜的镓(Ga)电镀方法和化学组合物。这些层可用于制造电子器件如薄膜太阳能电池。
[0008]在一个实施方案中,本发明提供了用于施加在导体上的溶液。该溶液包括Ga盐、络合剂和溶剂,其中该溶液通过电沉积在导体上提供亚微米厚的含Ga膜。
[0009]在本发明的另一实施方案中,该溶液还包括Cu盐和In盐中的一种或两种,且该溶液的pH值基本为7或更高。
[0010]在本发明的另一实施方案中,提供了在导体表面上获得具有亚微米厚度的含Ga膜的方法。
发明详述
[0011]本发明提供了以高沉积效率和可再现性在导电表面上电镀Ga膜的方法。本发明中所用的两种特定导电表面是Cu和In表面。通过在Cu和In表面上以有效方式电镀Ga,本发明可用于制造Cu/In/Ga、Cu/Ga/In、In/Ga/Cu和其它金属叠层,这些金属叠层进而可用于加工CIGS(S)型太阳能电池吸收体。
[0012]在这方面,本受让人(包括发明人)在薄膜太阳能电池技术中实现显著进步。已经出现铜-铟-硒化物(硫化物)或CIGS(S)和IBIIIAVIA族黄铜矿半导体系列中的相似材料,它们作为用于薄膜多晶太阳能电池应用的重要化合物。在最近开发出的用于生长CIGS(S)薄膜的“两步”加工法中,例如,在基底如涂覆有导电接触层的衬底上以含Cu、In和Ga的薄膜叠层如Cu/In/Ga、Cu/Ga/In、In/Cu/Ga、Ga/In/Cu、Ga/Cu/In、Cu/Ga/Cu/In、Cu/In/Cu/Ga等叠层的形式来电沉积受控量的Cu、In和Ga。这些叠层随后与Se和/或S反应以在接触层上形成CIGS(S)化合物的薄膜。这种处理方法的细节可见于下列专利申请,特此通过引用将其中每一篇并入本文:
[0013]2006年1月6日提交的美国临时申请No.60/756,750,名为“Precursor Copper Indium and Gallium for Selenide(Sulfide)Compound Formation”;
[0014]2006年3月14日提交的美国临时申请No.60/782,373,名为:“Method and Apparatus for Converting Precursor LayersInto Photovoltaic Absorbers”;
[0015]2006年3月14日提交的美国临时申请No.60/782,373,名为“Method and Apparatus for Converting Precursor Layers IntoPhotovoltaic Absorbers”;
[0016]2006年7月26日提交的美国临时申请No.60/820,479,名为“Technique for Doping Compound Layers Used In Solar CellFabrication”;
[0017]2005年3月15日提交的美国专利申请No.11/081,308,名为“Technique and Apparatus for Depositing Thin Layers ofSemiconductors For Solar Cell Fabrication”;
[0018]2005年11月2日提交的美国专利申请No.11/266,013,名为“Technique and Apparatus for Depositing Layers ofSemiconductors For Solar Cell and Module Fabrication”;和
[0019]2006年8月4日提交的美国专利申请No.11/462,685,名为“Technique For Preparing Precursor Films and Compound Layersfor Thin Film Solar Cell Fabrication and ApparatusCorresponding Thereto”。
[0020]应该认识到,在这种加工技术中,对沉积层如Cu、In和Ga层的厚度控制极其重要。这样的叠层中的Ga层厚度通常为亚微米,更通常为50-200纳米。化合物半导体如CIGS(S)的电学和光学性质对该材料的组成或化学计量比非常敏感。具体而言,这些性质强烈地取决于整个膜中的Cu/(In+Ga)和Ga/(Ga+In)摩尔比。在这样的化合物半导体层上制成的太阳能电池的效率进而取决于所述层的光学和电学性质。因此,采用Cu层、In层和Ga层中至少之一的两步加工和电沉积的太阳能电池制造方法的高生产率和可再现性强烈地取决于批次与批次之间(一个或多个)电镀层的沉积厚度的可再现性。此外,微观组成均匀性要求具有亚微米厚度的这些电沉积膜具有平滑形貌,具有通常小于膜厚度10%的表面粗糙度,并具有所需且可控的显微组织,这通常是具有亚微米尺寸晶粒的小晶粒显微组织。例如,采用具有粗糙表面形貌的Ga膜的叠层会造成整个膜中Ga含量在微观上的局部改变,尽管平均而言Ga含量可能在容许的范围内。应该指出,典型的可接受的CIGS(S)膜组合物具有0.8-1.0的Cu/(In+Ga)摩尔比,而Ga/(Ga+In)摩尔比可在0.1-0.3。
[0021]使用这些薄膜叠层,可以在包含衬底的基底上电镀或溅射沉积铜层(或In层),该衬底在其表面上可具有导电接触膜,如Mo层和/或含Ru的层。该衬底可以是金属箔、玻璃或者聚合物片或网。衬底表面上的含Ru的层可以是Ru层、Ru-合金层、Ru化合物层或者含Ru的叠层如Mo/Ru叠层或通常的M/Ru叠层,其中M是导体或半导体。可以使用本发明的电解液以各种电流密度如5、10、20、30、40和50mA/cm2在Cu表面(或In表面)上进行镓电镀。直流和/或可变(如脉冲或渐变(ramped))电压/电流波形都可用于电镀Ga层。
[0022]特别地,本发明提供了含络合剂的一类Ga镀覆浴。络合剂在该浴中络合Ga,形成可以通常表示为Gak+(Lm-)n的络合物。在镀覆过程中,可能发生Gak+(Lm-)n+ke-=Ga+nLm-的阴极反应,导致在阴极表面上沉积Ga并释放络合物质。“k”的值可为3。络合剂可以起到多种目的。其中包括:i)在该浴中降低游离Ga离子浓度,ii)减少Ga盐沉淀,和iii)维持稳定的pH。借助于络合剂,可以使Ga盐以0.1-1.0M的合理大的浓度溶于碱性溶液中而不沉淀,由此减少氢生成并提高沉积效率。本发明的浴组合物的一些优点是:i)由于pH值通常高于7,优选高于9,因此氢生成减少,ii)由于pH值优选低于14,避免了过度腐蚀问题,iii)络合的Ga物质以可再现的方式形成小晶粒的平滑Ga沉积物。
[0023]现在通过列举几个实施例来描述本发明。使用恒电位仪/恒电流仪(EG&G Model 263 A)进行这些实施例中的电镀实验。在镀覆过程中,搅拌溶液。用于镀覆试验的衬底包括不锈钢和钠钙玻璃,两者都涂覆有500纳米厚Mo层继之以厚度为5-100纳米的Ru层。首先,在Ru表面上电镀50-200纳米的Cu层。然后在Cu表面上电镀镓并评价结果。衬底表面积从几平方厘米到几百平方厘米不等,以理解该方法对大规模制造的适用性。在Ga沉积后,通过溶解该膜的各部分并使用原子吸收光谱法测量溶解的样品中的Ga量来评价均匀性和镀覆效率。
实施例1(柠檬酸盐作为络合剂):
[0024]制备含0.2-0.5M GaCl3和0.5-0.8M柠檬酸钠(Na3C6H5O7)的一组示例性水性镀覆浴。将pH值调节至10-13。以30-50mA/cm2的电流密度在铜表面上电沉积镓。对于100纳米厚度,获得表面粗糙度<10纳米的高附着性Ga膜。测量并发现镀覆效率在85-100%范围内,电流密度越高,则产生越有效的沉积过程。也使用含柠檬酸盐的络合浴在其它金属表面上镀覆镓。在Ru表面上的沉积直接产生75-90%的镀覆效率。在In表面上,Ga沉积效率达到100%。持续50小时的加速试验证明该浴的化学组合物稳定且没有任何氧化物/氢氧化物沉淀,且沉积效率可再现。
实施例2(EDTA作为络合剂):
[0025]用0.2M GaCl3和0.4摩尔EDTA配制水性镀覆浴。使用NaOH将pH值调节至12-14。以10-50mA/cm2的电流密度在电镀铜表面上进行镀覆试验。所有Ga膜都有光泽并具有平滑形貌。对于100纳米厚的膜,表面粗糙度<10纳米。在这种情形中发现,在大约20-30mA/cm2的电流密度下,与更低和更高的电流密度值相比,沉积效率较高。这些效率值在75-95%的范围内。
实施例3(甘氨酸作为络合剂):
[0026]用0.2M GaCl3和0.5M甘氨酸配制水性镀覆浴。使用NaOH将pH值调节至11-13。以10-50mA/cm2的电流密度在电镀铜表面上进行镀覆试验。所有Ga膜都有光泽并具有平滑表面。对于100纳米厚的层,表面粗糙度<10纳米。在这种情形中发现,在20-30mA/cm2下,沉积效率在75-90%的范围内。在更低和更高的电流密度值下,效率变低。
[0027]尽管在上述实施例中使用三种具体络合剂即柠檬酸盐、EDTA和甘氨酸来配制浴,但为补充或代替所述的络合剂,还可以使用具有羧基螯合基团和/或氨螯合基团的其它络合剂。所用柠檬酸盐可以是有机改性的,如柠檬酸三乙酯和柠檬酸三丁酯。其它络合剂包括但不限于,酒石酸盐(酯)(如酒石酸钠、酒石酸锂、酒石酸钾、酒石酸钠钾、酒石酸二乙酯、酒石酸二甲酯、酒石酸二丁酯、酒石酸二异丙酯和酒石酸铵)、草酸盐(如草酸钠、草酸钾和草酸锂)、氨和铵盐、乙二胺、次氨基三乙酸及其盐、羟乙基乙二胺三乙酸及其盐、氨基丁酸及其盐、氨基酸包括丙氨酸、缬氨酸、亮氨酸、异亮氨酸、脯氨酸(praline)、苯丙氨酸、酪氨酸、色氨酸、赖氨酸、精氨酸、组氨酸、天冬氨酸、谷氨酸盐、丝氨酸、苏氨酸(threomine)、半胱氨酸、蛋氨酸、天冬酰胺和谷氨酰胺。
[0028]应该注意,尽管一些所述络合剂甚至在酸性溶液中也表现良好,但本发明的优选Ga镀覆浴组合物具有高于7,优选高于9,且最优选为9-14的pH值。上述实施例使用以水为溶剂的简单水性化学组合物。尽管水是本发明优选的Ga镀覆浴配制剂中的优选溶剂,然而应理解,也可以在该配制剂中加入有机溶剂,其部分或完全替代水。这类有机溶剂包括但不限于甘油、醇类、乙二醇、碳酸乙烯酯、碳酸丙烯酯、乙腈、甲酰胺、二甲亚砜、环丁砜等。
[0029]上述实施例在Ga电沉积过程中采用直流电压/电流。应该注意,也可以利用脉冲或其它可变电压/电流源采用本发明的Ga镀覆浴以获得高镀覆效率和高品质的Ga沉积物。根据溶剂的性质,Ga电镀浴的温度可以为5-150℃。优选保持该温度低于溶剂的沸点。水基配制剂的优选浴温为10-60℃。最优选范围为15-30℃。
[0030]本发明的电镀浴可以包含附加成分。这些附加成分包括但不限于晶粒细化剂、表面活性剂、掺杂剂、其它金属或非金属元素等。例如,该配制剂中可以包括有机添加剂如表面活性剂、抑制剂、匀平剂(leveler)、加速剂等以便细化其晶粒组织和表面粗糙度。存在许多本领域中常用的此类添加剂。有机添加剂包括但不限于聚亚烷基二醇型聚合物、丙烷磺酸、香豆素、糖精、糠醛、丙烯腈、品红染料、胶粘剂、SPS、淀粉、右旋糖等。应该注意,该浴配制剂中可以包含其它材料以沉积Ga与其它材料的混合物或Ga-合金的薄层。例如,在该浴配制剂中添加Cu物质(例如硫酸铜、氯化铜等)允许沉积Cu-Ga合金和/或包含Cu和Ga的混合物的薄膜。类似地,可以在该配制剂中加入In以获得Ga-In合金和/或包含Ga和In的混合物的膜。以受控量添加In和Cu可以产生包含Cu、In和Ga的沉积物。也可以按允许沉积“掺杂Ga”膜的量添加掺杂剂。掺杂的Ga膜包含通常小于1原子%,优选小于0.1原子%的量的掺杂剂。这样的掺杂剂包括但不限于Na、Li、K、S、Se、Sb、P等。
[0031]使用本发明的浴组合物制成的Ga层用于在基底(该基底包括涂覆有Mo/Ru或仅Ru层的不锈钢衬底)上制造示例性全电镀金属叠层。这些叠层具有各种沉积次序以产生基底/Cu/Ga/In、基底/Cu/Ga/Cu/In、基底/Cu/In/Cu/Ga和基底/Cu/In/Ga结构。采用IndiumCorporation of America出售的氨基磺酸铟基镀覆浴用于In膜沉积。使该叠层于管式炉中在500℃下与Ar+H2Se气体混合物反应持续50分钟,形成Cu(In,Ga)Se2吸收体。使Cu/(In+Ga)摩尔比保持在0.88-0.94范围内,同时这些样品中的Ga/(Ga+In)摩尔比标称为30%。在反应步骤后,在吸收体表面上形成100纳米厚的CdS层,以产生基底/Cu(In,Ga)Se2/CdS结构。使用公知的化学浸渍法从包含硫酸镉、硫脲(Thiorea)、三乙胺(TEA)和氨的溶液沉积CdS。然后通过溅射技术在CdS膜上沉积ZnO/ITO透明导电层。通过在ITO层上蒸发Ni指形触点完成太阳能电池。由这些器件记录了高达11%的太阳能电池效率,证明了包含本发明的Ga层的电沉积叠层的品质。
Claims (53)
1.用于在导体上施加亚微米厚的含Ga膜的溶液,其包含:
Ga盐,
络合剂,
溶剂,且
其中该溶液在导体上提供亚微米厚的含Ga膜的电沉积。
2.权利要求1的溶液,其中该含Ga膜是基本纯净的Ga膜。
3.权利要求1的溶液,其中该溶液的pH值高于7.0。
4.权利要求3的溶液,其中Ga盐选自氯化镓、硫酸镓、乙酸镓和硝酸镓。
5.权利要求3的溶液,其中络合剂选自柠檬酸盐、EDTA和甘氨酸。
6.权利要求5的溶液,其中络合剂是柠檬酸钠、柠檬酸锂、柠檬酸铵、柠檬酸钾和有机改性的柠檬酸盐中的至少一种。
7.权利要求4的溶液,其中络合剂是柠檬酸钠、柠檬酸锂、柠檬酸铵、柠檬酸钾和有机改性的柠檬酸盐中的至少一种,其中溶剂是水且其中该溶液的pH值在9-14的范围内。
8.权利要求3的溶液,其中溶剂是水。
9.权利要求1的溶液,其中Ga盐选自氯化镓、硫酸镓、乙酸镓和硝酸镓。
10.权利要求1的溶液,其中络合剂选自柠檬酸盐、EDTA和甘氨酸。
11.权利要求10的溶液,其中络合剂是柠檬酸钠、柠檬酸锂、柠檬酸铵、柠檬酸钾和有机改性的柠檬酸盐中的至少一种。
12.权利要求11的溶液,其中溶剂是水。
13.权利要求1的溶液,其中溶剂是水。
14.权利要求1的溶液,还包含有机添加剂。
15.权利要求1的溶液,还包括Cu盐和In盐中的至少一种,且其中该溶液的pH值为7或更高。
16.权利要求15的溶液,其中该溶液的pH值在9-14的范围内。
17.权利要求15的溶液,其中该溶液基本不含任何VIA、VIIA和VIIIA族元素及其化合物。
18.权利要求17的溶液,其中络合剂选自柠檬酸盐、EDTA和甘氨酸。
19.权利要求1的溶液,还包括Cu盐和In盐两者,且其中该溶液的pH值为7或更高。
20.权利要求19的溶液,其中该溶液的pH值在9-14的范围内。
21.权利要求19的溶液,其中该溶液基本不含任何VIA、VIIA和VIIIA族元素及其化合物。
22.权利要求21的溶液,其中络合剂选自柠檬酸盐、EDTA和甘氨酸。
23.在导体表面上获得具有亚微米厚度的含Ga膜的方法,包括下列步骤:
获得包括Ga盐、络合剂和溶剂的溶液;
将该溶液施加到阳极和导体表面上,
在阳极和导体之间提供电势差,和
在导体表面上电沉积含Ga膜至亚微米厚度。
24.权利要求23的方法,其中该含Ga膜是基本纯净的Ga膜。
25.权利要求23的方法,其中导体是铜。
26.权利要求23的方法,其中导体是铟。
27.权利要求23的方法,其中在获得步骤中得到的溶液具有高于7.0的pH值。
28.权利要求27的方法,其中该溶液的pH值在9-14的范围内。
29.权利要求27的方法,其中在获得步骤中得到的溶液包含选自氯化镓、硫酸镓、乙酸镓和硝酸镓的Ga盐。
30.权利要求27的方法,其中在获得步骤中得到的溶液包含选自柠檬酸盐、EDTA和甘氨酸的络合剂。
31.权利要求30的方法,其中在获得步骤中得到的溶液包含柠檬酸钠、柠檬酸锂、柠檬酸铵、柠檬酸钾和有机改性的柠檬酸盐中的至少一种作为络合剂。
32.权利要求29的方法,其中在获得步骤中得到的溶液包含柠檬酸钠、柠檬酸锂、柠檬酸铵、柠檬酸钾和有机改性的柠檬酸盐中的至少一种作为络合剂,其中溶剂是水且其中该溶液的pH值在9-14的范围内。
33.权利要求27的方法,其中在获得步骤中得到的溶液包含水作为溶剂。
34.权利要求23的方法,其中在获得步骤中得到的溶液包含选自氯化镓、硫酸镓、乙酸镓和硝酸镓的Ga盐。
35.权利要求23的方法,其中在获得步骤中得到的溶液包含选自柠檬酸盐、EDTA和甘氨酸的络合剂。
36.权利要求35的方法,其中在获得步骤中得到的溶液包含柠檬酸钠、柠檬酸锂、柠檬酸铵、柠檬酸钾和有机改性的柠檬酸盐中的至少一种作为络合剂。
37.权利要求36的方法,其中在获得步骤中得到的溶液包含水作为溶剂。
38.权利要求23的方法,其中在获得步骤中得到的溶液包含水作为溶剂。
39.权利要求23的方法,其中在获得步骤中得到的溶液还包含有机添加剂。
40.权利要求23的方法,其中在获得步骤中得到的溶液还包括Cu盐和In盐中的至少一种,且其中该溶液的pH值为7或更高。
41.权利要求40的方法,其中该溶液的pH值在9-14的范围内。
42.权利要求41的方法,其中在获得步骤中得到的溶液基本不含任何VIA、VIIA和VIIIA族元素及其化合物。
43.权利要求42的方法,其中在获得步骤中得到的溶液包含选自柠檬酸盐、EDTA和甘氨酸的络合剂。
44.权利要求23的方法,其中在获得步骤中得到的溶液还包含Cu盐和In盐两者,且其中该溶液的pH值为7或更高。
45.权利要求44的方法,其中该溶液的pH值在9-14的范围内。
46.权利要求45的方法,其中在获得步骤中得到的溶液基本不含任何VIA、VIIA和VIIIA族元素及其化合物。
47.权利要求46的方法,其中在获得步骤中得到的溶液包含选自柠檬酸盐、EDTA和甘氨酸的络合剂。
48.用于在导体上施加亚微米厚的含Ga膜的溶液,其包含:
溶于溶剂中的Ga源,
络合剂,和
将该溶液的pH值调节至高于7的值的pH调节剂。
49.权利要求48的溶液,其中pH值高于10。
50.权利要求49的溶液,其中Ga源选自氯化镓、硫酸镓、乙酸镓和硝酸镓。
51.权利要求50的溶液,其中络合剂选自柠檬酸盐、EDTA和甘氨酸。
52.权利要求51的溶液,其中溶剂是水。
53.权利要求52的溶液,其中pH调节剂是NaOH和KOH中的至少一种。
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- 2007-09-25 EP EP07814990A patent/EP2094882A4/en not_active Withdrawn
- 2007-09-25 KR KR1020097008547A patent/KR20090085583A/ko not_active Application Discontinuation
- 2007-09-25 WO PCT/US2007/079356 patent/WO2008039736A1/en active Application Filing
- 2007-09-25 CN CNA2007800391728A patent/CN101528987A/zh active Pending
- 2007-09-27 TW TW096135964A patent/TW200829725A/zh unknown
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2009
- 2009-03-16 US US12/404,690 patent/US20090173634A1/en not_active Abandoned
Cited By (5)
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CN101805915A (zh) * | 2010-04-20 | 2010-08-18 | 南开大学 | 一种电镀金属Ga和Ga合金的溶液体系及其制备方法 |
CN102703928A (zh) * | 2012-05-23 | 2012-10-03 | 中国科学院过程工程研究所 | 一种超声辅助强化电解提取金属镓的方法 |
CN102703928B (zh) * | 2012-05-23 | 2015-04-01 | 中国科学院过程工程研究所 | 一种超声辅助强化电解提取金属镓的方法 |
CN112779013A (zh) * | 2020-12-31 | 2021-05-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | 用于光电化学刻蚀氮化镓的刻蚀液 |
CN112779013B (zh) * | 2020-12-31 | 2022-04-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | 用于光电化学刻蚀氮化镓的刻蚀液 |
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EP2094882A4 (en) | 2010-02-24 |
WO2008039736A1 (en) | 2008-04-03 |
US20090173634A1 (en) | 2009-07-09 |
TW200829725A (en) | 2008-07-16 |
US7507321B2 (en) | 2009-03-24 |
KR20090085583A (ko) | 2009-08-07 |
EP2094882A1 (en) | 2009-09-02 |
US20070272558A1 (en) | 2007-11-29 |
JP2010505045A (ja) | 2010-02-18 |
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