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Electrodeposition methods of gallium and gallium alloy films and related photovoltaic structures

A gallium alloy and photovoltaic device technology, applied in the field of gallium and gallium alloy films, can solve the problems of poor deposition morphology, high surface roughness, low cathode deposition efficiency, etc.

Active Publication Date: 2016-01-20
INT BUSINESS MASCH CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Hydrogen generation at the cathode results in a deposition efficiency below 100% because part of the deposition current is used to form hydrogen gas instead of forming a gallium film on the substrate or cathode
Low cathodic deposition efficiency due to excess hydrogen generation results in poor process repeatability, partly due to poor cathodic efficiency, and most importantly due to poor deposited films with high surface roughness and poor deposition morphology quality

Method used

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  • Electrodeposition methods of gallium and gallium alloy films and related photovoltaic structures
  • Electrodeposition methods of gallium and gallium alloy films and related photovoltaic structures
  • Electrodeposition methods of gallium and gallium alloy films and related photovoltaic structures

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0047] In this example, gallium is electroplated onto the film stack and then self-annealed to form an indium-rich indium gallium alloy. Plating chemistry contains 0.2MGa in 0.5MMSA 3+ , quenched with 0.5M NaOH, and then adjusted to a pH of 1.21 with an additional amount of MSA. Gallium was electroplated onto a 360nm layer of indium and a 250nm layer of copper. The gallium layer having a thickness of 150 nm was then self-annealed at room temperature of 18-22° C. for a period of 3 days. Once gallium is plated on indium, interdiffusion starts immediately and gradually forms In-Ga eutectic alloy.

[0048] Figure 7 Scanning electron micrograph showing a cross-sectional view of a film stack in which gallium was electrodeposited onto an indium layer and subsequently annealed to form an indium-rich gallium eutectic layer. Interestingly, Ga interdiffusion does not stop at the indium layer and continues into copper, forming CuInGa alloys.

example 2

[0050] In this example, various gallium baths with and without organic additives were used to electrodeposit gallium onto a glass substrate with a molybdenum layer that had previously been seeded with copper. The plating solution contained 0.25M gallium sulfate in 0.5MMSA with 0 and 500ppm thiourea. The electrolytic bath was at 18-20°C and stirred at 0 and 550 rpm. Use H 2 SO 4 , keeping the pH at 1.14.

[0051] The results showed that the presence of organic additives significantly accelerated gallium electroplating compared to baths that did not contain organic additives. Furthermore, continuous agitation of the electrolyte provided significantly higher current densities compared to no agitation. Figure 8 with 9 respectively graphs show that at 20mA / cm 2 and 30mA / cm 2 Surface topography view of a gallium film deposited galvanostatically. An increase in grain size was observed with increasing current density. No porosity was observed, and the film was uniform and ha...

example 3

[0053] In this example, the bath contains 0.2MGa in 0.5MMSA 3+ , quenched with 0.5M NaOH, then adjusted by adding more MSA to obtain a pH of 1.18. Include the various amounts of As indicated in the bath 2 o 3 . For not containing As 2 o 3 Or thiourea bath, the bath contains Ga in 0.5MMSA 3+ , quenched with 0.5M NaOH and adjusted to pH 1.18 with additional MSA. Contains As 2 o 3 As contained in the bath combined with thiourea 2 o 3 500-6000ppm and 100-1000ppm thiourea.

[0054] Figure 10 Overlays of various voltammograms are provided and include As 2 o 3 and thiourea combination data. As shown in the figure, As 2 o 3 The gradually increasing amount of provides a negative potential shift for the onset of the hydrogen evolution overpotential, thereby effectively suppressing the hydrogen generation. In addition, thiourea and As 2 o 3 The combination of accelerated gallium deposition.

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Abstract

Photovoltaic devices and methods of preparing p-type semiconductor layers for photovoltaic devices generally include electroplating a layer of gallium or a gallium alloy onto the conductive layer by contacting the conductive layer with a plating solution that does not contain a complexing agent, the plating solution comprising gallium salt, methanesulfonic acid or sodium sulfate, a solvent, and an organic additive comprising at least one nitrogen atom and / or at least one sulfur atom; adjusting the pH of the solution to less than 2.6 or greater than 12.6. The photovoltaic device includes: an impurity in the p-type semiconductor layer selected from arsenic, antimony, bismuth or mixtures thereof. By electroplating gallium or gallium alloys in this way, can be formed for the formation of CIS, CGS and CIGS? Various photovoltaic precursor layers for p-type semiconductor structures. A method of forming a gallium or gallium alloy thermal interface using an electroplating method is also disclosed.

Description

technical field [0001] The present invention generally relates to electrodeposition methods of gallium and gallium alloy films, such as those containing copper, indium, gallium and / or selenium, for use in thin film photovoltaic device fabrication and as thermal interface materials. Background technique [0002] For photovoltaic applications, two layers of semiconductor material with different properties are generally used to establish the electric field and the resulting current. The first layer is typically n-type semiconductor material and is generally thin to allow light to pass through to the underlying p-type semiconductor layer material, often referred to as the absorber layer. The combination of the absorber layer and the layer of n-type semiconductor material provides a suitable bandgap to absorb photons from the light source and generate high current and improved voltage. For the p-type layer, copper indium gallium diselenide semiconductor material (i.e., CuInGaSe ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01L31/032H01L31/0749H01L23/373H01L21/02C25D3/54
CPCC25D3/54C25D3/58C25D5/10H01L21/02568H01L21/02628H01L23/3738H01L31/0749Y02E10/541H01L2224/73253C25D7/126H01L31/0322C25D5/623C25D5/611H01L31/032C25D3/38C25D5/56
Inventor S·艾哈迈德H·德利吉安尼L·罗曼基夫K·罗伊特黄强R·瓦伊迪耶纳森
Owner INT BUSINESS MASCH CORP