CN103367134B - A kind of porous silicon surface metal electrode preparation method modified based on metal Ru - Google Patents
A kind of porous silicon surface metal electrode preparation method modified based on metal Ru Download PDFInfo
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- CN103367134B CN103367134B CN201310343200.2A CN201310343200A CN103367134B CN 103367134 B CN103367134 B CN 103367134B CN 201310343200 A CN201310343200 A CN 201310343200A CN 103367134 B CN103367134 B CN 103367134B
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Abstract
The invention discloses a kind of porous silicon surface metal electrode preparation method modified based on metal Ru, belong to Semiconductor Optoeletronic Materials and device arts, it comprises the following steps: 1. carry out metal-modified pre-treatment to porous silicon; 2. the acid solution of ruthenic chloride is used to modify porous silicon; 3. the porous silicon after modifying metal Ru carries out drying process; 4. the porous silicon surface deposit metal electrodes after metal Ru is modified; 5. short annealing; Photoetching is formed specifies electrode shape.The present invention utilizes noble metal decorated principle, through oxidation processes, form the transition zone of layer of metal ruthenium particle and silica at porous silicon surface, then evaporation metal electrode, the electrical contact quality between porous silicon and metal electrode can be improved, reduce the contact resistance of porous silicon and metal electrode.The present invention can be used for photodetector based on porous silicon and solar cell, effectively can improve response speed and the photoelectric conversion efficiency of device, and preparation technology is simple, cost is lower.
Description
Technical field
The present invention relates to Semiconductor Optoeletronic Materials and device arts, be specifically related to a kind of method improving metal and porous silicon semi-conductor electricity contact quality.
Background technology
1956, the electrolyte of Uhlir containing HF carried out electropolishing to monocrystalline silicon piece, and find to increase corrosion current within the specific limits, small particle can come off from silicon chip and be dissolved in electrolyte.From that time, people just to start in the aqueous solution of HF electrochemically corrosion of silicon and, to prepare porous silicon, and to be studied its character and application.Nineteen ninety, Canham reported first porous silicon film at room temperature can to send the great discovery of high efficiency visible ray.From that time, the sight of researchers has attracted on this porous material.Porous silicon due to have hole evenly, luminous efficient and polychrome and the feature such as at room temperature to work, make it in Display Technique and ultra high speed signal treatment technology, have very large application potential.
Since porous silicon self-discovery, the loose structure of its uniqueness, substantially increases the absorption to light; The preparation of porous silicon can be compatible with the integrated processing technology of existing silicon, can realize large-scale production.Therefore, the novel silicon base photodetector based on porous silicon has attracted the extensive concern of researchers.But the membrane electrode preparation of traditional silicon device, adopts the method for thermal evaporation and magnetron sputtering usually.Because porous silicon surface and inside exist a large amount of holes and cone-shaped structure, cause very high porosity and surface density of states, this will greatly reduce the electrical contact performance of porous silicon and film metal.Such as: 1, the existence of a large amount of hole weakens making the adhesive force between metal and porous silicon, and causes metal only at the exterior surface of porous silicon, may produce higher contact resistance; 2, very high surface density of states may cause the pinning effect of surperficial Fermi level, produces the potential barrier of block current flow, causes contact resistance to increase further, and show rectification characteristic.A large amount of results of study shows, by traditional evaporation and sputtering technology, is difficult to the electrical contact obtaining having low ohmic contact resistance and ohmic contact characteristic.
In order to make to obtain the low and stable ohmic contact of ohmic contact resistance between porous silicon and metal electrode, the root problem that needs solve is: how to reduce the potential barrier between porous silicon and metal electrode, improve the quality of gold half contact therebetween, to reach the object forming excellent Ohmic contact between metal and porous silicon.
Summary of the invention
For above-mentioned prior art, the object of the invention is to how to provide a kind of method improving metal and porous silicon semi-conductor electricity contact quality, it is intended to reduce the potential barrier between porous silicon and metal electrode, improve the quality of gold half contact therebetween, to reach the object forming excellent Ohmic contact between metal and porous silicon.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
Based on the porous silicon surface metal electrode preparation method that metal Ru is modified, it is characterized in that, comprise the following steps:
1. metal-modified pre-treatment is carried out to porous silicon;
2. metal Ru modifies porous area;
3. the porous silicon after modifying metal Ru carries out drying process;
4. the porous silicon surface deposit metal electrodes after metal Ru is modified;
5. short annealing;
6. photoetching is formed and specifies electrode shape.
This preparation method more detailed description is:
1. metal-modified pre-treatment is carried out to porous silicon surface: first adopt the HF aqueous solution to remove porous silicon surface oxide layer, then wash with deionized water;
2. ruthenium modifies porous area, and the acid solution that the porous silicon be about to after washing puts into ruthenic chloride invades bubble;
3. the porous silicon after modifying metal Ru carries out drying process, and the porous silicon surface after ruthenium is modified forms the transition zone of one deck ruthenium particle and silica;
4. deposit metal electrodes on the porous silicon surface after 3. processing through step;
5. short annealing process is carried out to the porous silicon after step 4. deposit metal electrodes;
Adopt photoetching process that metal electrode is etched into appointment electrode shape, complete electrode preparation.
As further improvement of the present invention: step 1. described in the concentration of HF solution be 10%, action time is 10s; Step 2. described in the RuCl of ruthenic chloride acid solution to be molar concentration be 0.01mol/L
3solution and molar concentration are the mixed liquor of the HCl solution of 40ml/L, and the reaction time is 30s ~ 60s.
As further improvement of the present invention: step 3. described in dry treatment temperature be 100 ~ 120 DEG C, the processing time is 10min, and the equipment of dry process is electric baking oven.
As further improvement of the present invention: step 4. described in deposition metal electrode thickness be 0.2 μm.
As further improvement of the present invention: step 5. described in short annealing treatment temperature be 300 ~ 500 DEG C, anneal 30s ~ 1min under an argon atmosphere.
Compared with prior art, the present invention has following beneficial effect:
One, the present invention utilizes the conductivity of metal Ru excellence, the transition zone of layer of metal ruthenium particle and silica is defined at porous silicon surface, and deposit metal electrodes on this basis, effectively can improve the electrical contact quality of metal electrode and porous silicon surface, reduce the potential barrier between metal/semiconductor, form the electric Ohmic contact of high contact quality.
Two, the present invention can be used for photodetector based on porous silicon and solar cell, effectively can improve response speed and the photoelectric conversion efficiency of device, and preparation technology is simple, cost is lower.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention.
Embodiment
Below in conjunction with the drawings and the specific embodiments, the invention will be further described.
A kind of porous silicon surface metal electrode preparation method modified based on metal Ru, it is characterized in that, comprise the following steps: 1. metal-modified pre-treatment is carried out to porous silicon surface: first adopt the HF aqueous solution to remove porous silicon surface oxide layer, then wash with deionized water; 2. metal Ru modifies porous area, and the acid solution that the porous silicon be about to after washing puts into ruthenic chloride invades bubble; 3. the porous silicon after modifying metal Ru carries out drying process, and the porous silicon surface after ruthenium is modified forms the transition zone of layer of metal ruthenium particle and silica; 4. deposit metal electrodes on the porous silicon surface after 3. processing through step; 5. short annealing process is carried out to the porous silicon after step 4. deposit metal electrodes; 6. adopt photoetching process that metal electrode is etched into appointment electrode shape, complete electrode preparation.
The porous silicon surface metal electrode preparation method of embodiment using Al as metal electrode.
Step 1: use the acid solution of ruthenic chloride to modify porous silicon: first adopt the HF aqueous solution to remove porous silicon surface oxide layer, the concentration of described HF solution is 10%, and action time is 10s; Step 2. described in ruthenic chloride acid solution for containing RuCl
3(0.01mol/L) and HCl(40ml/L) mixed liquor, the reaction time is 30s ~ 60s.Step 2: the porous silicon after modifying metal Ru carries out drying process, and sample is clean by washed with de-ionized water, and puts into roaster drying, and baking temperature is 110 DEG C, and the processing time is 10min.Step 3: short annealing, at temperature 300 ~ 500 DEG C and argon gas atmosphere condition, annealing 30s ~ 1min.Step 4: adopt photoetching process that metal electrode is etched into appointment electrode shape, completes electrode preparation.
Claims (5)
1., based on the porous silicon surface metal electrode preparation method that metal Ru is modified, it is characterized in that, preparation method is:
1. metal-modified pre-treatment is carried out to porous silicon surface: first adopt the HF aqueous solution to remove porous silicon surface oxide layer, then wash with deionized water;
2. ruthenium modifies porous area, and the acid solution that the porous silicon be about to after washing puts into ruthenic chloride soaks;
3. the porous silicon after modifying metal Ru carries out drying process, and the porous silicon surface after ruthenium is modified forms the transition zone of one deck ruthenium particle and silica;
4. deposit metal electrodes on the porous silicon surface after 3. processing through step;
5. short annealing process is carried out to the porous silicon after step 4. deposit metal electrodes; Adopt photoetching process that metal electrode is etched into appointment electrode shape, complete electrode preparation.
2. the porous silicon surface metal electrode preparation method modified based on metal Ru according to claim 1, is characterized in that, step 1. described in the concentration of HF solution be 10%, action time is 10s; Step 2. described in the RuCl of ruthenic chloride acid solution to be molar concentration be 0.01mol/L
3solution and molar concentration are the mixed liquor of the HCl solution of 40ml/L, and the reaction time is 30s ~ 60s.
3. the porous silicon surface metal electrode preparation method modified based on metal Ru according to claim 1, is characterized in that, step 3. described in dry treatment temperature be 100 ~ 120 DEG C, the processing time is 10min, and the equipment of dry process is electric baking oven.
4. according to claim 1 based on metal Ru modify porous silicon surface metal electrode preparation method, it is characterized in that, step 4. described in deposition metal electrode thickness be 0.2 μm.
5. according to claim 1 based on metal Ru modify porous silicon surface metal electrode preparation method, it is characterized in that, step 5. described in short annealing treatment temperature be 300 ~ 500 DEG C, anneal 30s ~ 1min under an argon atmosphere.
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| CN105572815B (en) * | 2015-12-21 | 2018-02-23 | 华进半导体封装先导技术研发中心有限公司 | Active optics pinboard and optical interconnection module |
| US10141155B2 (en) * | 2016-12-20 | 2018-11-27 | Kla-Tencor Corporation | Electron beam emitters with ruthenium coating |
Citations (5)
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|---|---|---|---|---|
| CN1613160A (en) * | 2002-01-03 | 2005-05-04 | 尼电源系统公司 | Porous fuel cell electrode structures having conformal electrically conductive layers thereon |
| CN1754276A (en) * | 2001-04-19 | 2006-03-29 | 尼能源系统公司 | Porous silicon and sol-gel derived electrode structures and assemblies adapted for use with fuel cell systems |
| CN101111927A (en) * | 2005-01-27 | 2008-01-23 | 国际商业机器公司 | Gate stack engineering by electrochemical processing utilizing through-gate-dielectric current flow |
| US7968248B2 (en) * | 2007-01-31 | 2011-06-28 | Junli Liu | Liquid-liquid fuel cell systems having flow-through anodes and flow-by cathodes |
| CN103151424A (en) * | 2013-03-12 | 2013-06-12 | 电子科技大学 | Method for preparing metal electrode on surface of porous silicon by using improved chemical plating process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1754276A (en) * | 2001-04-19 | 2006-03-29 | 尼能源系统公司 | Porous silicon and sol-gel derived electrode structures and assemblies adapted for use with fuel cell systems |
| CN1613160A (en) * | 2002-01-03 | 2005-05-04 | 尼电源系统公司 | Porous fuel cell electrode structures having conformal electrically conductive layers thereon |
| CN101111927A (en) * | 2005-01-27 | 2008-01-23 | 国际商业机器公司 | Gate stack engineering by electrochemical processing utilizing through-gate-dielectric current flow |
| US7968248B2 (en) * | 2007-01-31 | 2011-06-28 | Junli Liu | Liquid-liquid fuel cell systems having flow-through anodes and flow-by cathodes |
| CN103151424A (en) * | 2013-03-12 | 2013-06-12 | 电子科技大学 | Method for preparing metal electrode on surface of porous silicon by using improved chemical plating process |
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