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Publication numberCN101094935 A
Publication typeApplication
Application numberCN 200580045339
PCT numberPCT/JP2005/023892
Publication date26 Dec 2007
Filing date27 Dec 2005
Priority date28 Dec 2004
Also published asEP1889945A1, US20080032044, WO2006070799A1
Publication number200580045339.2, CN 101094935 A, CN 101094935A, CN 200580045339, CN-A-101094935, CN101094935 A, CN101094935A, CN200580045339, CN200580045339.2, PCT/2005/23892, PCT/JP/2005/023892, PCT/JP/2005/23892, PCT/JP/5/023892, PCT/JP/5/23892, PCT/JP2005/023892, PCT/JP2005/23892, PCT/JP2005023892, PCT/JP200523892, PCT/JP5/023892, PCT/JP5/23892, PCT/JP5023892, PCT/JP523892
Inventors栗谷川悟, 田中良明
Applicant昭和砚壳石油株式会社
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Mothod for producing zno-based transparent electroconductive film by MOCVD(metal organic chemical vapor deposition) method
CN 101094935 A
Abstract
A method for producing a ZnO-based transparent electroconductive film by MOCVD (metal organic chemical vapor deposition) method using diethyl zinc having a low purity (99.99 to 98 % or 99.99 to 90 %) as a raw material, which comprises using steam (H<SUB>2</SUB>O) as an oxidizing agent and diverting the triethylaluminum contained in the raw material as an impurity to an additive (and further adding diborane as another additive), and effecting a vapor phase reaction among the above diethyl zinc, the above steam (H<SUB>2</SUB>O) and triethylaluminum (and diborane). The above method utilizes the triethylaluminum contained as an impurity in a moderately-priced diethyl zinc raw material having a low purity, as an additive, and thus can be suitably employed for producing the above film at a reduced cost.
Claims(6)  translated from Chinese
1.一种制备ZnO透明导电膜的方法,其中将低纯度二乙基锌(Zn(C2H5)2)用作通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的原料,其中所述方法包括使用90-99.99%的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂,利用作为杂质以0.01-10%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,和加入二硼烷(B2H6)作为第III族元素添加剂,以使所述二乙基锌、所述水蒸气(H2O)、所述三乙基铝和所述二硼烷经历汽相反应,并从而通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜。 1. A method of preparing ZnO transparent conductive film, wherein the low purity of diethylzinc (Zn (C2H5) 2) is used by MOCVD (metal organic chemical vapor deposition) Preparation of raw materials ZnO transparent conductive film, wherein said method comprising the use of 90 to 99.99% of diethyl zinc and water vapor is used as the starting material (H2O) as an oxidizing agent, in order to utilize as an impurity contained in an amount of 0.01 to 10% diethyl zinc in the triethylaluminum (Al (C2H5) 3) as a group III element additives, and added diborane (B2H6) as a group III element additives, such that the diethylzinc, the water vapor (H2O), the triethylammonium aluminum base and said diborane undergo vapor-phase reaction, and thus by MOCVD (metal organic chemical vapor deposition) Preparation of ZnO transparent conductive films.
2.一种制备ZnO透明导电膜的方法,其中将低纯度二乙基锌(Zn(C2H5)2)用作通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的原料,其中所述方法包括使用99.99-98%的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂,利用作为杂质以0.01-2%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,和加入少量的二硼烷(B2H6)作为第III族元素添加剂,以使所述二乙基锌、所述水蒸气(H2O)、所述三乙基铝和所述二硼烷经历汽相反应,并从而通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜。 2. A process for preparing ZnO transparent conductive film, wherein the low purity of diethylzinc (Zn (C2H5) 2) is used by MOCVD (metal organic chemical vapor deposition) Preparation of raw materials ZnO transparent conductive film, wherein said method comprising the use of 99.99-98% of diethyl zinc and water vapor is used as the starting material (H2O) as an oxidizing agent, in order to utilize as an impurity contained in an amount of 0.01 to 2% of the diethyl zinc triethylaluminum (Al (C2H5) 3) as a group III element additives, and small amounts of diborane (B2H6) as a group III element additives, such that the diethylzinc, the water vapor (H2O), the triethylaluminum and diborane through the vapor phase reaction, and thus by MOCVD (metal organic chemical vapor deposition) of ZnO transparent conductive film.
3.一种制备ZnO透明导电膜的方法,其中将低纯度二乙基锌(Zn(C2H5)2)用作通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的原料,其中所述方法包括使用90-98%的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂,和利用作为杂质以2-10%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,以在不加入二硼烷(B2H6)作为第(III族元素添加剂的情况下,使所述二乙基锌、所述水蒸汽(H2O)和所述三乙基铝经历汽相反应,并从而通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜。 3. A method of preparing ZnO transparent conductive film, wherein the low purity of diethylzinc (Zn (C2H5) 2) is used by MOCVD (metal organic chemical vapor deposition) Preparation of raw materials ZnO transparent conductive film, wherein said method comprising the use of 90-98% of diethyl zinc and water vapor is used as the starting material (H2O) as an oxidizing agent, and to use as an impurity contained in an amount of 2-10% of the diethyl zinc triethyl aluminum (Al (C2H5) 3) as a group III element additive was not added to the diborane (B2H6) as under (III-element additive case, so that the diethylzinc, the water vapor (H2O Preparation) and triethylaluminum undergo the vapor phase reaction, and thus by MOCVD (metal organic chemical vapor deposition) ZnO transparent conductive film.
4.根据权利要求3的通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的方法,其中所述的沉积在基板温度为150-190℃和包含所述二乙基锌的载气对包含所述水蒸气(H2O)的载气的流速比为0.95-1.05的条件下进行。 4. The 3 by MOCVD (Metal Organic Chemical Vapor Deposition) method of ZnO transparent conductive film, wherein said deposited at a substrate temperature of 150-190 ℃ and comprising the diethylzinc contained claim said gas containing water vapor (H2O) in the carrier gas flow rate ratio is carried out under conditions of 0.95 to 1.05.
5.一种制备ZnO透明导电膜的方法,其中将低纯度二乙基锌(Zn(C2H5)2)用作通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的原料,其中所述方法包括使用99.99-98%的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂,和利用作为杂质以0.01-2%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,以在不加入二硼烷(B2H6)作为第(III族元素添加剂的情况下,使所述二乙基锌、所述水蒸气(H2O)和所述三乙基铝经历汽相反应,并从而通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜。 5. A method of preparing ZnO transparent conductive film, wherein the low purity of diethylzinc (Zn (C2H5) 2) is used by MOCVD (metal organic chemical vapor deposition) Preparation of raw materials ZnO transparent conductive film, wherein said method comprising the use of 99.99-98% of diethyl zinc and water vapor is used as the starting material (H2O) as an oxidizing agent, and to use as an impurity contained in an amount of 0.01 to 2% of the diethyl zinc triethyl aluminum (Al (C2H5) 3) as a group III element additive was not added to the diborane (B2H6) as under (III-element additive case, so that the diethylzinc, the water vapor (H2O Preparation) and triethylaluminum undergo the vapor phase reaction, and thus by MOCVD (metal organic chemical vapor deposition) ZnO transparent conductive film.
6.根据权利要求5的通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的方法,其中所述的沉积在基板温度为160-180℃和包含所述二乙基锌的载气对包含所述水蒸气(H2O)的载气的流速比为约1.0的条件下进行。 By MOCVD 5 according to claim (Metal Organic Chemical Vapor Deposition) method of ZnO transparent conductive film, wherein said deposition at a substrate temperature of 160-180 ℃ and containing the diethylzinc contained the flow rate of gas containing the vapor of (H2O) ratio of carrier gas under conditions of about 1.0 was.
Description  translated from Chinese
通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的方法 By MOCVD (metal organic chemical vapor deposition) method of ZnO transparent conductive film

技术领域 FIELD

本发明涉及制备用于CIS型薄膜太阳能电池等的ZnO透明导电膜的方法。 The present invention relates to a method for preparing CIS type thin-film solar cell, a ZnO transparent conductive film.

背景技术 BACKGROUND

用于形成透明导电膜的方法是已知的,其中通过化学汽相淀积法(CVD法)形成太阳能电池用的透明导电膜(参见,例如,专利文献1)。 The method for forming the transparent conductive film are known, in which a transparent conductive film for a solar cell by a chemical vapor deposition method (CVD method) is formed (see, e.g., Patent Document 1). 这个方法包括将作为原料的有机锌化合物(例如二乙基锌)、氧化剂(例如水或水蒸气)和添加剂(例如作为铝的三乙基铝和作为硼的二硼烷)引入到包含加热至约60-350℃,优选100-200℃(特定地为约150℃)的基板的反应室中,从而形成在所述基板上的氧化锌膜。 This method comprises an organic zinc compound as the raw material (e.g., diethyl zinc), an oxidizing agent (e.g., water or water vapor) and an additive (e.g., an aluminum triethyl aluminum and boron as diborane) is introduced into the containing heated to about 60-350 ℃, preferably 100-200 ℃ (specifically from about 150 ℃) substrate in the reaction chamber, thereby forming a zinc oxide film on the substrate. 将第III族元素(例如作为铝的三乙基铝和作为硼的二硼烷)加入到氧化锌中使电阻率降低。 The Group III element (e.g., an aluminum triethyl aluminum and diborane as a boron) was added to zinc oxide manipulation reduced electrical resistivity. 包含氢的氧化锌膜比包含铝的氧化锌膜具有更低的热稳定性,而包含铝的氧化锌膜比包含氢的氧化锌膜具有稍微更高的电阻率。 Zinc oxide film containing hydrogen than the zinc oxide film containing aluminum has a lower thermal stability, while zinc oxide film containing aluminum ratio of zinc oxide film containing hydrogen has a somewhat higher resistivity. 尽管专利文献1公开了作为原料的有机锌化合物的二乙基锌的使用,但其没有说明所述原料的纯度。 Although Patent Document 1 discloses, as a raw material of the organic zinc compound diethylzinc use, but it has no description of the purity of the starting material.

专利文献1:JP-B-6-14557通常,在通过化学汽相淀积法(CVD法)形成ZnO透明导电膜的情况下,将具有被称为半导体级纯度的99.999-99.9999%纯度的二乙基锌用作原料。 Patent Document 1: JP-B-6-14557 In general, in the case of the ZnO transparent conductive film formed by a chemical vapor deposition method (CVD method), and will be referred to a semiconductor having a purity level of 99.999-99.9999% purity di diethyl zinc as a raw material. 因为用于除去杂质的纯化步骤是必须的,所以所述二乙基锌的成本是高的。 Since the purification step for removing impurities is necessary, so the cost of the diethyl zinc is high. 这导致形成ZnO透明导电膜的成本是高的。 This results in cost ZnO transparent conductive film is high. 另外,由于在通过化学汽相淀积法(CVD法)形成ZnO透明导电膜的情况下为了降低ZnO透明导电膜的电阻率而加入的二硼烷是其操作必须使用特殊设备的特殊材料气体,因此这导致了生产成本增加。 Further, since in the case of the ZnO transparent conductive film formed by a chemical vapor deposition method (CVD method) in order to reduce the resistance of the ZnO transparent conductive film while the diborane is added to its operation must use special equipment and special material gas, This therefore leads to increased production costs.

发明内容 SUMMARY

本发明要解决的技术问题本发明的第一个目的是提供通过MOCVD(金属有机化学汽相淀积)法形成ZnO透明导电膜的方法,该方法利用廉价的低纯度二乙基锌(Zn(C2H5)2)作为原料,并从而降低了形成ZnO透明导电膜的成本。 A first object of the present invention to solve the technical problem of the present invention to provide a method by MOCVD (Metal Organic Chemical Vapor Deposition) method of forming a ZnO transparent conductive film, the method using an inexpensive low-purity diethylzinc (Zn ( C2H5) 2) as a starting material, and thus reducing the cost of the formation of the ZnO transparent conductive film. 通过本发明的方法形成的ZnO透明导电膜在性能上(电阻率和消光系数)与形成自高纯度二乙基锌作为原料的ZnO透明导电膜是一样的。 ZnO transparent conductive film formed by the method of the present invention (resistivity and extinction coefficient) and formed from high purity of diethylzinc in performance as a transparent conductive ZnO film material is the same.

本发明的第二个目的是在通过MOCVD(金属有机化学汽相淀积)法的膜形成中通过利用作为杂质包含于所述廉价低纯度原料二乙基锌中的三乙基铝(Al(C2H5)3)作为添加剂而减少添加剂的使用和将其引入的操作和降低膜形成的成本。 A second object of the present invention is by MOCVD (metal organic chemical vapor deposition) film forming method by utilizing inexpensive as impurities contained in low purity of the starting material diethylzinc triethyl aluminum (Al ( C2H5) 3) as an additive to reduce the use of additives which are incorporated in and operating costs and lower film. 由本发明方法形成的ZnO透明导电膜在性能上(电阻率和消光系数)与通过其中使用高纯度二乙基锌作为原料和加入三乙基铝(Al(C2H5)3)的方法形成的ZnO透明导电膜是一样的。 ZnO transparent conductive film formed by the method of the present invention on the properties (resistivity and extinction coefficient) and by which a high-purity ZnO diethyl zinc as the starting material and triethylaluminum (Al (C2H5) 3) The method of forming a transparent the conductive film is the same.

本发明的第三个目的是通过由其中不加入(使用)二硼烷(B2H6)的MOCVD(金属有机化学汽相淀积)法形成ZnO透明导电膜降低形成ZnO透明导电膜的成本,所述二硼烷已经在相关现有技术的沉积方法中用作添加剂并且其为操作必须使用特殊的设备的特殊材料气体。 A third object of the present invention is not added by the wherein (use) diborane (B2H6) of MOCVD (metal organic chemical vapor deposition) method is formed to reduce the cost of ZnO transparent conductive film formed of ZnO transparent conductive film, the diborane deposition method has been used in the related art as additives and it must use special equipment and special material gases. 通过本发明的这个方法形成的ZnO透明导电膜在性能上(电阻率和消光系数)与通过其中使用高纯度二乙基锌作为原料和加入作为其操作必须使用特殊的设备的特殊材料气体的二硼烷(B2H6)的方法形成的ZnO透明导电膜是一样的。 ZnO transparent conductive film formed by the method of the present invention on the properties (resistivity and extinction coefficient) and through which a high purity as the starting material, and diethyl zinc was added as its operation must use special equipment and special material gas bis ZnO transparent conductive film borane (B2H6) is a method of forming the same.

解决问题的手段(1)用于消除如上所述问题的本发明提供制备ZnO透明导电膜的方法,其中将低纯度二乙基锌(Zn(C2H5)2)用作通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的原料,其中所述方法包括使用90-99.99%的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂,利用作为杂质以0.01-10%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,和加入二硼烷(B2H6)作为第III族元素添加剂,以使所述二乙基锌、所述水蒸气(H2O)、所述三乙基铝和所述二硼烷经历汽相反应,并从而通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜。 Means for Solving the Problem (1) is used to eliminate the problem described above, the present invention provides a transparent conductive film of ZnO, wherein the low purity of diethylzinc (Zn (C2H5) 2) is used by MOCVD (Metal Organic Chemical Vapor Deposition) Preparation of raw materials ZnO transparent conductive film, wherein said method comprises using 90 to 99.99% of diethyl zinc and water vapor is used as the starting material (H2O) as an oxidizing agent, use as an impurity in an amount of 0.01 to 10% contained in the diethylzinc in the triethylaluminum (Al (C2H5) 3) as a group III element additives, and added diborane (B2H6) as a group III element additives, such that the diethyl zinc, the water vapor (H2O), the triethylaluminum and the diborane undergo vapor phase reaction, and thus by MOCVD (metal organic chemical vapor deposition) of ZnO transparent conductive film.

(沉积法I:高纯度范围用于例如电流驱动装置(大电流量),例如太阳能电池,和低纯度范围用于例如电压驱动装置(小电流量),例如液晶显示器面板和防止静电聚积)(2)本发明提供制备ZnO透明导电膜的方法,其中将低纯度二乙基锌(Zn(C2H5)2)用作通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的原料,其中所述方法包括使用99.99-98%的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂,利用作为杂质以0.01-2%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,和加入少量的二硼烷(B2H6)作为第III族元素添加剂,以使所述二乙基锌、所述水蒸气(H2O)、所述三乙基铝和所述二硼烷经历汽相反应,并从而通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜。 (Deposition I: High purity range, for example the current driving device (large amount of current), such as solar cells, and low purity range, for example, a voltage drive (a small amount of current), such as a liquid crystal display panel and prevent buildup of static charges) ( 2) The present invention provides a ZnO transparent conductive film prepared by a method in which the low purity of diethylzinc (Zn (C2H5) 2) is used by MOCVD (metal organic chemical vapor deposition) Preparation of raw materials ZnO transparent conductive film, wherein said method comprises using 99.99-98% of diethyl zinc and water vapor is used as the starting material (H2O) as an oxidizing agent, in order to utilize as an impurity contained in an amount of 0.01 to 2% of the diethyl zinc triethyl aluminum (Al (C2H5) 3) as a group III element additives, and small amounts of diborane (B2H6) as a group III element additives, such that the diethylzinc, the water vapor (H2O), the said triethylaluminum and diborane undergo the vapor phase reaction, and thus by MOCVD (metal organic chemical vapor deposition) of ZnO transparent conductive film.

(沉积法II:用于高纯度范围或电流驱动装置)(3)本发明提供制备ZnO透明导电膜的方法,其中将低纯度二乙基锌(Zn(C2H5)2)用作通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的原料,其中所述方法包括使用90-98%的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂,和利用作为杂质以2-10%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,以使所述二乙基锌、所述水蒸气(H2O)和所述三乙基铝经历汽相反应,并从而通过其中不加入二硼烷(B2H6)作为第III族元素添加剂的MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜。 (Deposition Method II: for the range of high purity or the current driving means) (3) The present invention provides a transparent conductive film of ZnO, wherein the low purity of diethylzinc (Zn (C2H5) 2) is used by MOCVD (metal Organic Chemical Vapor Deposition) Preparation of raw materials ZnO transparent conductive film, wherein said method comprises using 90-98% of diethyl zinc and water vapor is used as the starting material (H2O) as an oxidizing agent, and used as an impurity to 2- contained in an amount of 10% diethyl zinc in said triethyl aluminum (Al (C2H5) 3) as a group III element additives, such that the diethylzinc, the water vapor (H2O) and the said triethylaluminum undergo vapor phase reaction, and thus is not added by which diborane (B2H6) as a Group III element additive MOCVD (metal organic chemical vapor deposition) of ZnO transparent conductive film.

(沉积法III:用于低纯度范围或电压驱动装置)(4)本发明提供如在上述(3)下描述的通过如上述(2)下描述的MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的方法,其特征在于所述的沉积在基板温度为150-190℃和包含所述二乙基锌的载气对包含所述水蒸气(H2O)的载气的流速比为0.95-1.05的条件下进行。 (Deposition Method III: purity range or for low voltage drive means) (4) The present invention provides as in the above (3) as (2) under the above described description of MOCVD (metal organic chemical vapor deposition) method Preparation of ZnO transparent conductive film, characterized in that said deposited at a substrate temperature of 150-190 ℃ and diethylzinc comprising said carrier gas containing the vapor (H2O) in the carrier gas flow rate ratio 0.95-1.05 conducted under conditions.

(沉积法III:用于低纯度范围或电压驱动装置)(5)本发明提供制备ZnO透明导电膜的方法,其中将低纯度二乙基锌(Zn(C2H5)2)用作通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的原料,其中所述方法包括使用99.99-98%的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂,和利用作为杂质以0.01-2%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,以使所述二乙基锌、所述水蒸气(H2O)和所述三乙基铝经历汽相反应,并从而通过其中不加入二硼烷(B2H6)作为第III族金属添加剂的MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜。 (Deposition Method III: low purity range or a voltage drive means for) (5) The present invention provides a transparent conductive film of ZnO, wherein the low purity of diethylzinc (Zn (C2H5) 2) is used by MOCVD (metal Organic Chemical Vapor Deposition) Preparation of raw materials ZnO transparent conductive film, wherein said method comprises using 99.99-98% of diethyl zinc and water vapor is used as the starting material (H2O) as an oxidizing agent, and used as an impurity to 0.01 2% of the amount of the diethylzinc contained in the triethylaluminum (Al (C2H5) 3) as a group III element additives, such that the diethylzinc, the water vapor (H2O) and the said triethylaluminum undergo vapor phase reaction, and thus is not added by which diborane (B2H6) as a Group III metal additive MOCVD (metal organic chemical vapor deposition) of ZnO transparent conductive film.

(沉积法IV:用于液晶显示器面板、防雾玻璃和防静电玻璃,并用于低纯度范围或电压驱动装置)(6)本发明提供如在上述(5)下描述的通过如上述(4)下所述的MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的方法,其中所述的沉积在基板温度为160-180℃和包含所述二乙基锌的载气对包含所述水蒸气(H2O)的载气的流速比为约1.0的条件下进行。 (Deposition Method IV: a liquid crystal display panel, anti-fog and anti-static glass glass, and or voltage range for low purity drive means) (6) The present invention provides as in the above (5) as described by the above (4) Under the MOCVD (metal organic chemical vapor deposition) method of ZnO transparent conductive film, wherein said deposited at a substrate temperature of 160-180 ℃ and diethylzinc comprising said carrier gas containing the said water vapor (H2O) in the carrier gas flow rate ratio is carried out under conditions of about 1.0.

(沉积法IV:用于液晶显示器面板、防雾玻璃和防静电玻璃,并用于低纯度范围或电压驱动装置)有益效果本发明提供通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜的方法,其利用廉价的低纯度二乙基锌(Zn(C2H5)2)作为原料,并可因此降低形成ZnO透明导电膜的成本。 (Deposition Method IV: a liquid crystal display panel, anti-fog and anti-static glass glass, and or voltage range for low purity drive means) to provide the beneficial effects of the present invention prepared by MOCVD (Metal Organic Chemical Vapor Deposition) ZnO transparent conductive The method of film, using an inexpensive low-purity diethylzinc (Zn (C2H5) 2) as a raw material, and thus reducing the cost of the transparent conductive film ZnO is formed. 通过本发明的方法形成的ZnO透明导电膜在性能上(电阻率和消光系数)与形成自高纯度二乙基锌作为原料的ZnO透明导电膜是一样的。 ZnO transparent conductive film formed by the method of the present invention (resistivity and extinction coefficient) and formed from high purity of diethylzinc in performance as a transparent conductive ZnO film material is the same.

本发明在通过MOCVD(金属有机化学汽相淀积)法的膜形成中通过利用作为杂质包含于所述廉价低纯度原料二乙基锌中的三乙基铝作为添加剂,消除了添加剂的使用和将其引入的操作并降低了膜形成的成本。 In the present invention, by MOCVD (metal organic chemical vapor deposition) film forming method by utilizing inexpensive as impurities contained in low purity of the starting material diethylzinc triethyl aluminum as an additive, to eliminate the use of additives and introduction into operation and reduces the cost of film formation. 由本发明的这个方法形成的ZnO透明导电膜在性能上(电阻率和消光系数)与通过其中使用高纯度二乙基锌作为原料和加入三乙基铝(Al(C2H5)3)的方法形成的ZnO透明导电膜是一样的。 ZnO transparent conductive film on the properties (resistivity and extinction coefficient) and by the use of high purity wherein diethyl zinc as the starting material and triethylaluminum (Al (C2H5) 3) a method of forming by the forming process of the present invention ZnO transparent conductive film is the same.

本发明通过由其中不加入(使用)二硼烷(B2H6)的MOCVD(金属有机化学汽相淀积)法形成ZnO透明导电膜可降低形成ZnO透明导电膜的成本,所述二硼烷已经在相关现有技术的沉积法中用作添加剂并且其为操作必须使用特殊的设备的特殊材料气体。 Wherein the present invention is not added by the (used) diborane (B2H6) of MOCVD (metal organic chemical vapor deposition) method is formed ZnO ZnO transparent conductive film to reduce the cost of forming the transparent conductive film, said diborane has Related prior art deposition method and it is used as an additive operation must use special equipment and special material gases. 通过本发明的这个方法形成的ZnO透明导电膜在性能上(电阻率和消光系数)与通过其中使用高纯度二乙基锌作为原料和加入作为其操作必须使用特殊的设备的特殊材料气体的二硼烷(B2H6)的方法形成的ZnO透明导电膜是一样的。 ZnO transparent conductive film formed by the method of the present invention on the properties (resistivity and extinction coefficient) and through which a high purity as the starting material, and diethyl zinc was added as its operation must use special equipment and special material gas bis ZnO transparent conductive film borane (B2H6) is a method of forming the same.

附图说明 Brief Description

图1说明在通过MOCVD(金属有机化学汽相淀积)法形成ZnO透明导电膜的本发明的方法中加入二硼烷的情况下,电阻率和消光系数随二乙基锌的纯度的变化而改变。 Figure 1 illustrates the changes added diborane in the process method is formed by MOCVD (Metal Organic Chemical Vapor Deposition) ZnO transparent conductive film of the present invention, the resistivity and the extinction coefficient with a purity of diethylzinc and change.

图2说明在通过MOCVD(金属有机化学汽相淀积)法形成ZnO透明导电膜的本发明的方法中不加入二硼烷的情况下,电阻率和消光系数随在二乙基锌中三乙基铝(TEAl)的加入量的变化而改变。 Figure 2 illustrates a method under the law is formed by MOCVD (Metal Organic Chemical Vapor Deposition) ZnO transparent conductive film of the present invention was not added diborane case, resistivity and extinction coefficient with triethylamine in diethyl zinc yl aluminum (TEAl) is added in an amount changed by the change.

附图标记说明I:采用90-99.99%的二乙基锌作为原料,水蒸气作为氧化剂,以及TEAI和二硼烷作为添加剂的沉积法II:采用99.99-98%的二乙基锌作为原料,水蒸气作为氧化剂,以及TEAl和二硼烷作为添加剂的沉积法III:采用90-98%的二乙基锌作为原料,水蒸气作为氧化剂,以及TEAl作为添加剂的沉积法IV:采用99.99-98%的二乙基锌作为原料,水蒸气作为氧化剂,以及TEAl作为添加剂的沉积法TEAl:三乙基铝具体实施方式本发明涉及制备ZnO透明导电膜的方法,其中将低纯度二乙基锌(Zn(C2H5)2)作为原料以通过MOCVD(金属有机化学汽相淀积)法制备ZnO透明导电膜。 Reference Numerals I: use of 90-99.99% of diethyl zinc as the starting material, water vapor as the oxidizing agent, and TEAI and diborane as an additive deposition method II: the use of 99.99-98% of diethylzinc as starting materials, water vapor as the oxidizing agent, and TEAl and diborane as an additive deposition method III: use 90-98% of diethyl zinc as the starting material, water vapor as the oxidizing agent, as well as deposition IV TEAl additive: the use of 99.99-98% diethylzinc as starting materials, water vapor as the oxidizing agent, and as an additive deposition method TEAl TEAl: triethylaluminum DETAILED DESCRIPTION The present invention relates to a ZnO transparent conductive film, wherein the low purity diethyl zinc (Zn (C2H5) 2) as a raw material by MOCVD (metal organic chemical vapor deposition) Preparation of ZnO transparent conductive films.

通常,在通过化学汽相淀积法(CVD法)形成ZnO透明导电膜的情况下,为此待用作有机锌化合物原料的二乙基锌是被称为半导体级的、已经被高度纯化和具有99.999-99.9999%纯度的种类。 Typically, in the case of the ZnO transparent conductive film formed by a chemical vapor deposition method (CVD method), for which the organic zinc compound to be used as starting material is known as diethylzinc is semiconductor grade, has been highly purified and with a wide 99.999-99.9999% purity. 然而,在本发明的方法中,使用已经被低程度纯化的低纯度二乙基锌,例如具有纯度为90%或更高的二乙基锌或具有纯度为98%或更高的二乙基锌。 However, in the method of the present invention, a low degree of purification has been the use of low-purity diethylzinc, e.g., having a purity of 90% or more of diethyl zinc or with a purity of 98% or more of diethyl zinc.

通过MOCVD(金属有机化学汽相淀积)法形成ZnO透明导电膜的本发明的方法包括使用90-99.99%的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂,利用作为杂质以0.01-10%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,和加入二硼烷(B2H6)作为第III族元素添加剂,以使所述二乙基锌、所述水蒸气(H2O)、所述三乙基铝和所述二硼烷经历汽相反应,并从而制备ZnO透明导电膜。 The method of the present invention by MOCVD (Metal Organic Chemical Vapor Deposition) method of forming a ZnO transparent conductive film include use of 90-99.99% of diethyl zinc and water vapor is used as the starting material (H2O) as an oxidizing agent, used as an impurity to 0.01 -10% by weight of the diethylzinc contained in the triethylaluminum (Al (C2H5) 3) as a group III element additives, and added diborane (B2H6) as a group III element additives, such that The diethylzinc, the water vapor (H2O), the triethylaluminum and diborane through the vapor phase reaction, and thereby preparing a transparent conductive ZnO film. (下文中,这个方法被称为沉积法I。)在上述的用于形成ZnO透明导电膜的沉积法I中,当使用具有在上述可用的二乙基锌的纯度范围中处于高纯度范围的98-99.99%的纯度的二乙基锌时,然后利用作为杂质以0.01-2%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂,和加入二硼烷(B2H6)作为第III族元素添加剂,以使所述二乙基锌、所述水蒸气(H2O)、所述三乙基铝和所述二硼烷经历汽相反应,并从而制备ZnO透明导电膜。 (Hereinafter, this method is called deposition I.) In the deposition method I described above for the formation of the ZnO transparent conductive film, when used in a high purity having the above-mentioned range is available in a range of purity of diethylzinc in When 98-99.99% purity of diethylzinc, and then to use as an impurity contained in an amount of 0.01 to 2% diethyl zinc in said triethyl aluminum (Al (C2H5) 3) as the Group III element additives, and added diborane (B2H6) as a group III element additives, such that the diethylzinc, the water vapor (H2O), the triethylaluminum and diborane through the vapor phase reaction and thereby preparing a transparent conductive ZnO film. (下文中,这个方法被称为沉积法II。)在其中如沉积法I和沉积法II中那样加入二硼烷(B2H6)用于膜形成的情况下,随着所述二乙基锌的纯度被降低(三乙基铝的含量增加)至约99%,所述电阻率和所述消光系数分别倾向于增加和降低,如图1中所示的那样。 (Hereinafter, this method is called deposition II.) In which the deposition such as deposition method I and method II as added diborane (B2H6) for the case of film formation, with the diethylzinc Purity is reduced (triethylaluminum content increases) to about 99%, the resistivity and the extinction coefficient tends to increase and decrease, respectively, as shown in FIG. 1. 这被认为是因为硼B的掺杂作用(并入的硼的比例)由于并入的铝的量的增加而降低。 This is considered to be because the effect of doping of boron B (boron incorporated proportion) due to the increased amount of aluminum incorporated is reduced. 当所述纯度降低至约97%时,铝被以较大的量被并入,并且因此,所述电阻率和消光系数分别降低和增加。 When the purity decreased to about 97%, the aluminum is to be incorporated in significant amounts, and thus, the extinction coefficient and resistivity decreased and increased, respectively. 对应于这些范围的膜各自被认为具有使所述膜实际上可用作透明导电膜的性质。 Corresponding to each of these ranges is believed to have a film so that the film is actually used as a transparent conductive film properties.

通过沉积法I(利用具有纯度为90-99.99%的二乙基锌作为原料)形成的ZnO透明导电膜可被用于如下应用中。 By a deposition method I (having a purity of 90 to 99.99% utilization of diethyl zinc as the starting material) ZnO transparent conductive film can be used in the following applications. 对应于所述高纯度范围的那些可用于电流驱动装置(大电流量),例如,太阳能电池,而对应于低纯度范围的那些可用于电压驱动装置(用于小电流量),例如,液晶显示器面板和防止静电聚积。 Range corresponding to the high purity of the current driving means that can be used (large amount of current), for example, a solar cell, and corresponding to a low range of purity that can be used for voltage driving means (for small amount of current), for example, a liquid crystal display panel and prevent static electricity buildup.

例如,利用具有纯度为98%的二乙基锌获得的具有厚度为约1.4μm的透明导电膜的性质包括薄层电阻为14.6Ω/□,和可见光透过率为90.1%。 For example, the use of having a purity of 98% diethyl zinc in nature having a thickness of about 1.4μm of the transparent conductive film obtained include sheet resistance 14.6Ω / □, and visible light transmittance was 90.1%. 该膜可以是实用的透明导电膜。 The film may be a practical transparent conductive film.

通过沉积法II(利用具有纯度为99.99-98%的二乙基锌作为原料)形成的ZnO透明导电膜可用于太阳能电池,因为它们具有太阳能电池应用要求的2-20Ω/□的薄层电阻范围。 By a deposition method II (having a purity of 99.99-98% utilization of diethyl zinc as the starting material) ZnO transparent conductive film can be used for solar cells, solar cell application because they have the required sheet resistance range 2-20Ω / □ of .

例如,当在膜形成中使用具有纯度为98%的二乙基锌和以约20sccm/600sccm所述二乙基锌的量加入二硼烷时,获得的透明导电膜具有厚度为约1.4μm,和薄层电阻为9Ω/□,和可见光透过率为89.4%。 For example, when having a purity of 98% diethyl zinc in film formation and to about 20sccm / 600sccm the amount of diethylzinc was added diborane, the transparent conductive film obtained has a thickness of about 1.4μm, and sheet resistance 9Ω / □, and visible light transmittance was 89.4%. 这些膜的性能可被认为与具有厚度为约1.4μm,利用具有纯度为约99.999%的二乙基锌作为原料形成的,包括薄层电阻为8.1Ω/□,和可见光透过率为88.1%的透明导电膜是几乎相同的。 The performance of these membranes can be considered to have a thickness of about 1.4μm, the use of having a purity of about 99.999% diethyl zinc is formed as a raw material, including the sheet resistance of 8.1Ω / □, and visible light transmittance was 88.1% The transparent conductive film was nearly the same. 该透明导电膜的性能足以用于太阳能电池的应用。 The transparent conductive film of sufficient performance for a solar cell applications.

用于通过MOCVD(金属有机化学汽相淀积)法(其中不加入作为第III族元素添加剂的二硼烷(B2H6)的方法)形成ZnO透明导电膜的本发明的另一个方法说明于下。 Another method for the ZnO transparent conductive film by the MOCVD (Metal Organic Chemical Vapor Deposition) method (which is not added as a Group III element additive diborane (B2H6) method) formed according to the present invention will be described in the following.

使用具有90-98%的低纯度的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂。 Having 90-98% of the low-purity diethylzinc used as a raw material and water vapor (H2O) as an oxidizing agent. 将作为杂质以2-10%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂。 As impurities 2-10% by weight of the diethylzinc contained in the triethylaluminum (Al (C2H5) 3) as a group III element additive. 将所述二乙基锌、所述水蒸气(H2O)、所述三乙基铝经历汽相反应,以从而制备ZnO透明导电膜,其中不加入二硼烷(B2H6)作为第III族元素添加剂。 The diethylzinc, the water vapor (H2O), the triethylaluminum undergo vapor phase reaction to thereby prepare a ZnO transparent conductive film, which was not added diborane (B2H6) as a Group III element additive . (下文中,该方法被称为沉积法III。)在所述沉积法III中,所述的沉积在基板温度为150-190℃和包含所述二乙基锌的载气对包含所述水蒸气(H2O)的载气的流速比为0.95-1.05的条件下进行。 (Hereinafter, this method is called deposition, III.) III in the deposition process, the deposition at the substrate temperature of 150-190 ℃ and diethylzinc comprising said carrier gas containing the water the flow rate of steam (H2O) of the carrier gas ratio of 0.95 to 1.05 in the next condition.

用于通过MOCVD(金属有机化学汽相淀积)法(其中不加入作为第III族元素添加剂的二硼烷(B2H6)的方法)形成ZnO透明导电膜的本发明的另一个方法说明于下。 Another method for the ZnO transparent conductive film by the MOCVD (Metal Organic Chemical Vapor Deposition) method (which is not added as a Group III element additive diborane (B2H6) method) formed according to the present invention will be described in the following.

使用具有99.99-98%的低纯度的二乙基锌作为原料和使用水蒸气(H2O)作为氧化剂。 99.99-98% having a low purity of diethylzinc and water vapor is used as the starting material (H2O) as an oxidizing agent. 将作为杂质以0.01-2%的量包含于所述二乙基锌中的三乙基铝(Al(C2H5)3)作为第III族元素添加剂。 As impurities contained in an amount of 0.01 to 2% diethyl zinc in said triethyl aluminum (Al (C2H5) 3) as a group III element additive. 将所述二乙基锌、所述水蒸气(H2O)、所述三乙基铝经历汽相反应,以从而制备ZnO透明导电膜,其中不加入二硼烷(B2H6)作为第III族元素添加剂。 The diethylzinc, the water vapor (H2O), the triethylaluminum undergo vapor phase reaction to thereby prepare a ZnO transparent conductive film, which was not added diborane (B2H6) as a Group III element additive . (下文中,该方法被称为沉积法IV。)在所述沉积法IV中,所述的沉积在基板温度为160-180℃和包含所述二乙基锌的载气对包含所述水蒸气(H2O)的载气的流速比为约1.0的条件下进行。 (Hereinafter, this method is called deposition IV.) IV in the deposition process, the deposition at the substrate temperature of 160-180 ℃ and diethylzinc comprising said carrier gas containing the water the flow rate of steam (H2O) ratio of carrier gas under conditions of about 1.0 was.

通过所述沉积法IV形成的ZnO透明导电膜具有如图2中所示的那些性质,并可用于例如CIS型薄膜太阳能电池用的低电阻透明导电膜的应用中。 ZnO transparent conductive film formed by the deposition method IV of those having properties as shown in Figure 2, and can be applied, for example, CIS type thin film solar cell with a low-resistance transparent conductive film.

如在沉积法III和沉积法IV中那样,在不加入二硼烷(B2H6)进行沉积的情况下,通过加入(存在)少量的三乙基铝(TEAl)可将所述电阻率降低至约1/5,000,而不必加入二硼烷(B2H6),如图2所示。 As above, without the addition of diborane (B2H6) deposition of the case, by the addition of (presence) a minor amount of triethylaluminum (TEAl) can be reduced to the resistivity in deposition III and IV in about deposition method 1 / 5,000, without added diborane (B2H6), as shown in Fig. 当以较大的量加入TEAl时,所述电阻率倾向于逐步增加,这是由过量的杂质使膜品质降低导致的。 When a large amount is added TEAl, the resistivity tends to gradually increase, which is an excessive amount of impurities resulting in decreased quality of the film. 然而,这些膜在一些应用中用作实际应用的透明导电膜足够了。 However, these films as a transparent conductive film of practical application is sufficient in some applications. 随着所加入的三乙基铝(TEAl)的量增加,所述消光系数增加,因为通过所述添加剂的光吸收增加了。 With the added amount of triethylaluminum (TEAl) increases, the extinction coefficient increases, because light absorption by the additive increases. 然而,从如上给出的试验数据可以推断当所加入的TEAl的量高达约10%时可形成保持透明性的导电薄膜。 However, the experimental data given above it can be inferred from the transparency of the conductive thin film can be formed when the amount added is TEAl up to about 10%.

通过沉积法III(采用具有纯度为90-98%的二乙基锌作为原料;加入的三乙基铝(TEAl)的量为10-2%)形成的ZnO透明导电膜具有如图2中所示的那些性质。 By a deposition method III (having a purity of 90-98% using diethyl zinc as a raw material; added amount of triethylaluminum (TEAl) is 10-2%) ZnO transparent conductive film 2 formed as having those properties shown. 这些膜具有相对高的电阻率(10-1,000Ω/□)并可用于例如液晶显示器、防雾玻璃和防静电玻璃的应用中。 These films have a relatively high resistivity (10-1,000Ω / □) and a liquid crystal display applications, for example, anti-fog and anti-static glass in the glass.

例如,通过其中加入(包含)3%TEAl的方法(使用具有纯度为97%的二乙基锌)形成的约1.11μm厚的透明导电膜具有薄层电阻为107Ω/□,和可见光透过率为88.9%。 For example, by added thereto (including) 3% TEAl method (having a purity of 97% diethyl zinc) of about 1.11μm thick transparent conductive film having a sheet resistance of 107Ω / □, and visible light transmittance 88.9%. 在这种情况下,如果具有较高的光透过率的膜是必须的,将膜厚降低至约0.1μm预计可获得薄层电阻为1,000Ω/□,和可见光透过率为97%或更高。 In this case, if the film has a high light transmittance is necessary to reduce the film thickness of about 0.1μm is expected to obtain a sheet resistance of 1,000Ω / □, and visible light transmittance of 97% or higher.

通过沉积法IV(利用具有纯度为99.99-98%的二乙基锌作为原料;加入的三乙基铝(TEAl)的量为2-0.01%)形成的ZnO透明导电膜具有如图2中所示的那些性质。 By a deposition method IV (having a purity of 99.99-98% utilization of diethyl zinc as a raw material; adding an amount of triethylaluminum (TEAl) is 2-0.01%) ZnO transparent conductive film 2 formed as having those properties shown. 这些膜可用于例如CIS型薄膜太阳能电池用的低电阻透明导电膜的应用中。 These films can be used such as application CIS type thin film solar cell using a low-resistance transparent conductive film.

例如,通过其中加入(包含)0.6%TEAl的方法(使用具有纯度为99.4%的二乙基锌)形成的约1.16μm厚的透明导电膜具有薄层电阻为18Ω/□,和可见光透过率为91.7%。 For example, by added (containing) 0.6% TEAl method (having a purity of 99.4% diethyl zinc) of about 1.16μm thick transparent conductive film having a sheet resistance of 18Ω / □, and visible light transmittance 91.7%. 由于在太阳能电池中使用的透明导电膜为具有薄层电阻为约2-20Ω/□的透明导电膜,因此所述透明导电膜被认为是可实际应用于太阳能电池中。 Since the transparent conductive film used in solar cell having a sheet resistance of about 2-20Ω / □ transparent conductive film, and therefore the transparent conductive film is considered to be actually used in solar cells.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
CN103805960A *7 Nov 201221 May 2014北京有色金属研究总院Preparation method of chrome oxide thin film
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International ClassificationH01B13/00, H01L31/04, C23C16/40
Cooperative ClassificationY02E10/50, H01L31/1884, C23C16/407
European ClassificationH01L31/18J, C23C16/40L
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