CN102201531A

CN102201531A - Solution for surface metallization pretreatment of semiconductor P/N type refrigerating sheet and application method of same

Info

Publication number: CN102201531A
Application number: CN2011100879299A
Authority: CN
Inventors: 王艺臻
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-04-08
Filing date: 2011-04-08
Publication date: 2011-09-28

Abstract

The invention discloses a solution for the surface metallization pretreatment of a semiconductor P/N type refrigerating sheet and an application method of the same. In the invention, the solution consists of the following components in percentage by volume: 5-52% of hydrochloric acid, 5-36% of nitric acid, 0-28g/L of surfactant and the remaining of water. As the surface metallization pretreatment is performed on the semiconductor P/N type refrigerating sheet by using the solution disclosed by the invention, the rejection rate of the semiconductor P/N type refrigerating sheet can be reduced, the application of a metal nickel material is reduced, and the technical process of the surface metallization pretreatment can also be shortened to reduce the production cost; and moreover, the bonding force of a base material and a metallized layer can be increased, and the temperature difference and performances of the refrigerating sheet can be improved.

Description

A kind of solution and using method that is used for the pre-treatment of semiconductor P/N type cooling piece surface metalation

Technical field

The present invention relates to the material metal technical field, be specifically related to the metallization technology field of semiconductor cooling material.

Background technology

The metallization process of the P/N section bar material of using at semiconductor chilling plate, usually the processing mode that adopts be physical treatment process (gram A. Luo Wenhaimu in the Fried. one zero three teaching and research rooms of Beijing Aeronaution College translate. modern plating [M]. Beijing: China Machine Press, 1982.; Wang Li, Yu Xiufa, Liu Xinhong. the research of thermoelectric material sheet process of surface treatment. power technology .26,441 (2002).; Gu Xiaojie. the master thesis .2003 of Harbin Institute of Technology), promptly to semiconductor material surface with sandblast after spray nickel technology or clean the surface that the method for back spray nickel is handled material, to improve the adhesion of coating, but because high temperature and high pressure that sandblast and spray nickel produce can cause wafer breakage, make product percent of pass low, production efficiency is low, and then increases cost.

Make the field for the conductor refrigeration sheet, metallization itself to semi-conducting material does not draw attention, relevant research and patent are seldom, the comparatively successful hydrofluoric acid of wherein studying that Shanghai Shenhe Thermo-magenetic Electronic Co., Ltd.'s invention is arranged, nitric acid, mixing coarsening solution (the Wang Li of dodecyl sodium sulfate, Yu Xiufa, Liu Xinhong. the research of thermoelectric material sheet process of surface treatment. power technology .26,441 (2002) .) and Harbin Institute of Technology's utilization membrane removal, reduction, sensitization, the method for chemical nickel plating after the preimpregnation/zinc-plated (Gu Xiaojie. the master thesis .2003 of Harbin Institute of Technology).In addition, though also have document (Jiang Yusi, farsighted. the application of sufacing in semiconductor cooler. Guangdong non-ferrous metal journal .15,46 (2005).; Chen Liangjie. the research of the direct nickel plating of semiconductor refrigerating crystal. electroplate and environmental protection .23 15 (2003) .) the mixed acid system was carried out research, but and fail to obtain good effect.

Summary of the invention

The objective of the invention is to problems such as the product percent of pass that exists in the metallization technology according to the conventional semiconductor material is low, production efficiency is low, a kind of semiconductor P/N type refrigerating sheet surface metalation pre-treatment solution is provided, by using this solution that rupture rate and the deformation rate of P/N type wafer in metallization processes reduced, improve the qualification rate and the production efficiency of product, reduce cost.

The object of the invention is achieved by the following technical programs:

A kind of solution that is used for the pre-treatment of semiconductor P/N type refrigerating sheet surface metalation, form by following component: the hydrochloric acid of 5 ~ 52 volume %, the nitric acid of 5 ~ 36 volume %, the surfactant of 0 ~ 28g/L, surplus is a water.

The present invention has strong oxidizing property after having used nitric acid and mixed in hydrochloric acid, concrete utilization semiconductor chilling plate is with material when (containing tellurium, selenium, bismuth, antimony element), can control its corrosion rate preferably, obtain roughness surface uniformly, thereby strengthen the adhesion of metal layer and ground thereafter greatly.Clearly, it is a kind of indirect processes that traditional handicraft is used sandblast/spray nickel/electroplating technique, and after the present invention successfully uses chemical method processing semi-conducting material, gets final product Direct Electroplating.

As technical scheme further, above-mentioned surfactant is dodecyl sodium sulfate or dodecyl sodium sulfonate potassium.

Use pre-treatment solution of the present invention to be used for the pre-treatment of semiconductor P/N type refrigerating sheet surface metalation, comprise the steps: semiconductor P/N type refrigerating sheet through oil removing, washing, immerse in the pre-treatment solution, be 12 ~ 36 ℃ in temperature and take out behind processing 30s ~ 100min down, washing, promptly.

Compared with prior art, the present invention has following beneficial effect:

1, reduced sandblast and spray nickel step, flow process is shorter, and cost is lower; After adopting patent of the present invention, estimate to reduce 300RMB/10000pcs (equaling 2.7 centimetres of calculations),, meet green spirit of producing simultaneously because patent technology of the present invention power consumption is also less with wafer diameter at the cost of human cost and spray nickel;

2, the present invention uses chemicals commonly used, and more environmental protection and safety also must be trained especially to operating personnel, and Comparatively speaking, prescription corrosivity, risk and the contaminative of the hydrofluoric acid of use are all bigger;

3, solution hydrofluoric acid of the present invention is volatile, and drug consumption can be bigger than the present invention, and cost is better;

4, the method flow of chemical nickel plating is longer, and is complicated chemistry systems, and control is difficulty comparatively; And that the present invention controls is simple and easy;

5, after solution-treated of the present invention, the material surface roughness is more even, and is better with binding force of cladding material.(use the traditional handicraft adhesion to be the 80N/6.25 square millimeter, use patent of the present invention after adhesion be promoted to the 150N/6.25 square millimeter);

6, use solution-treated of the present invention after, performance that can enhance device, outstanding behaviours can increase the device temperature difference, uses that the thermal gradient energy of cooling piece increases about 1.6 degrees centigrade after the patent of the present invention;

7, the wafer that obtains after the solution-treated of the present invention, deformation rate is lower, yields is higher, traditional handicraft metallization step scrappage is about 3%, use patent of the present invention after, scrappage almost is reduced to zero.

Description of drawings

Fig. 1 is the P after handling among the embodiment 1 and the surperficial crystalline phase figure of N type wafer;

Fig. 2 is the P after handling among the embodiment 2 and the surperficial crystalline phase figure of N type wafer;

Fig. 3 is the P after handling among the embodiment 3 and the surperficial crystalline phase figure of N type wafer.

Embodiment

Further explain the present invention below in conjunction with embodiment, but embodiment does not do any type of qualification to the present invention.

Embodiment 1

2.7 centimetres of diameters, thick 0.15 centimetre wafer (P type or N type), after oil removing, after the washing, immerse 8% (volume) hydrochloric acid, 5%(volume) surfactant (particularly dodecyl sodium sulfate or dodecyl sodium sulfonate potassium) of nitric acid and 3g/L, all the other are water, after handling 30 seconds～100 minutes down, 12 ~ 36 ℃ of temperature take out washing, it is more even to obtain the littler surface of roughness, roughness for use reduced 10 ~ 40% before the technology of the present invention after, can change over to such as metallization process such as electronickelling or sputter (Fig. 1).

Embodiment 2

2.7 centimetres of diameters, thick 0.15 centimetre wafer (P type or N type), after oil removing, after the washing, immerse 28% (volume) hydrochloric acid, 30%(volume) surfactant (particularly dodecyl sodium sulfate or dodecyl sodium sulfonate potassium) of nitric acid and 15g/L, all the other are water, after handling 30 seconds ~ 100 minutes down, 12 ~ 36 ℃ of temperature take out washing, it is more even to obtain the littler surface of roughness, roughness for use reduced 10 ~ 40% before the technology of the present invention after, can change over to such as metallization process such as electronickelling or sputter (Fig. 2).

Embodiment 3

2.54 centimetres of diameters, thick 0.15 centimetre wafer (P type or N type), after oil removing, after the washing, immerse 10% (volume) hydrochloric acid, 18%(volume) surfactant (particularly dodecyl sodium sulfate or dodecyl sodium sulfonate potassium) of nitric acid and 10g/L, all the other are water, after handling 30 seconds～100 minutes down, 12 ~ 36 ℃ of temperature take out washing, it is more even to obtain the littler surface of roughness, roughness for use reduced 10 ~ 40% before the technology of the present invention after, can change over to such as metallization process such as electronickelling or sputter (Fig. 3).

Embodiment 4 characteristic tests

Roughness concentration:

Use roughmeter, setting sample length respectively is 0.6mm and 2.0mm, and roughness indexs such as measure R a, Rz are relatively used the roughness of the example 1-3 sample before and after the technology of the present invention.Comparing data sees table 1 for details.

Table 1 roughness ratio

By provide among above table 1 data and the accompanying drawing 1-3 accordingly based on the sample surfaces figure of crystalline phase microscope (Olympus BX51), can find out handle through this patent after, the sample roughness reduces, evenness increases.

Tensile test:

The tensile test condition is that to randomly draw 5 diameters on the wafer of diameter 2.54 be 2.5 millimeters hole, and with the tin layer welding after thin copper wire and this some metallization, and by the tensiometer test, on average pulling force is that 120N is qualified.

Table 2 tensile test relatively

Figure 2011100879299100002DEST_PATH_IMAGE003

By above data can find out use this patent technology after, binding force of cladding material is promoted to 167.4N by 79.8N.The product refrigeration temperature difference:

The semiconductor refrigerating sheet device temperature difference relatively after being assembled into device after being assembled into device after the traditional handicraft metallization and using the present invention to metallize.

Table 3 temperature difference relatively

Temperature difference technology	The temperature difference 1	The temperature difference 2	The temperature difference 3	The temperature difference 4	The temperature difference 5	Mean temperature difference
							Traditional handicraft	65.3	66.8	67.8	66.3	67.3	66.7
Example 1	68.3	68.1	69.3	68.3	68.2	68.44
							Example 2	68.2	67.8	69.2	68.2	68.3	68.34
Example 3	67.2	68.2	69	68.1	69.3	68.36

Can find out that by above data after the use this patent technology, after being assembled into device, maximum temperature difference can increase about 1.6 degree.

To sum up characteristic test result, patent of the present invention can obtain the uniform pre-treatment of stable roughness surface, and then significantly strengthen the adhesion of metal layer, finally show the performance that has strengthened the semiconductor chilling plate device, particularly improved its temperature difference performance, improved the temperature difference and also mean the efficient that increases device.Thereby patent of the present invention is the achievement that has business efficiency.

Claims

1. solution that is used for the pre-treatment of semiconductor P/N type refrigerating sheet surface metalation is characterized in that being made up of following component: the hydrochloric acid of 5 ~ 52 volume %, and the nitric acid of 5 ~ 36 volume %, the surfactant of 0 ~ 28g/L, surplus is a water.

2. the solution that is used for the pre-treatment of semiconductor P/N type refrigerating sheet surface metalation according to claim 1 is characterized in that described surfactant is dodecyl sodium sulfate or dodecyl sodium sulfonate potassium.

3. the using method of any described pre-treatment solution of claim in the claim 1 ~ 2, it is characterized in that comprising the steps: semiconductor P/N type refrigerating sheet through oil removing, washing, immerse in the pre-treatment solution, be 12 ~ 36 ℃ in temperature and take out behind processing 30s ~ 100min down, washing, promptly.