CN101307453B - Technology of silicon nano-wires without electrodeposit nickel and thermoelectric power device based on the technology - Google Patents
Technology of silicon nano-wires without electrodeposit nickel and thermoelectric power device based on the technology Download PDFInfo
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- CN101307453B CN101307453B CN2008100379417A CN200810037941A CN101307453B CN 101307453 B CN101307453 B CN 101307453B CN 2008100379417 A CN2008100379417 A CN 2008100379417A CN 200810037941 A CN200810037941 A CN 200810037941A CN 101307453 B CN101307453 B CN 101307453B
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Abstract
The invention discloses a technology for electroless deposition of nickel on a silicon nano line and a thermoelectric power device based on the technology. The manufacturing technique of the thermoelectric power device is compatible with the MEMS technique, and the thermoelectric power device mainly adopts the electrochemical etching method and is low in cost, simple in operation and easy to realize. The technology is mainly to synthesize a silicon nano line array on crystalline silicon materials at a room temperature; the average height of the nano line is about 30 mu m and the mean diameter is about 40 nanometers; the procedure reduces the thermal conductivity and the temperature diffusion coefficient of the materials, strengthens the quantum size effect of the silicon nano line and improves the thermionic emission capacity; a nano nickel film is deposited on the silicon nano line through the electroless nickel plating technology and nickel and silicon form good ohmic contact at the time, thereby the technology further strengthens the thermo-electronic emission capacity and reduces the internal resistance of a thermoelectric structure; and electroless plating solution is a non-phosphate formulation, thereby formation of alloy by phosphate and the nickel is avoided and then the thermo-electronic emission efficiency is reduced. Moreover, about porous silicon with depth 200 mu m is etched on the other surface of a silicon chip and an aluminum film is coated on the surface of the silicon chip by means of vaporization; because the structure has large specific surface area and depth-width ratio, the adiathermancy of the materials is further increased; and simultaneously a Schottky barrier is generated on a contact surface of aluminum and the silicon, thereby the thermal electromotive force of the thermoelectric structure is increased.
Description
Technical field
The present invention relates to a kind of research of thermoelectric (al) power switching device, be specially a kind of thermoelectric (al) power element manufacturing, belong to micro-nano thermoelectric (al) power switch technology field based on electroless deposition nickel technology on the silicon nanowires.
Technical background
Along with the continuous development of the micro-nano processing technology of MEMS, with the focus that micro-nano thermoelectric (al) power conversion electric power become people's research of can integrated going up of ic process compatibility.Brand-new green energy resource with advantages such as low cost, high-energy-density, microminiaturization, long service life, safety performance are good is the target that the scientific research personnel pursues, and especially utilize the temperature gradient field of organism and surrounding space and other hot machine used heat or sun power and circumstance of temperature difference to generate electricity concerning people is a kind of technical challenge always.The thermoelectric (al) power material of existing report is because of bulky, and perhaps factor such as complex manufacturing technology or material expensive is difficult to widespread adoption.Though the body silicon materials do not possess thermoelectric property, but the silicon nanowires of the about 50nm of diameter just can make its thermal conductivity reduce 100 times than body silicon, and its specific surface area compares the increase that body silicon has tens orders of magnitude, so may have the potentiality of making higher thermoelectric figure of merit (ZT) thermoelectric (al) power device based on the composite nanostructure of silicon nanowires and metallic substance.The ZT here is the criterion of thermoelectrical efficiency, and it is the function of material Seebeck coefficient S, conductivity, thermal conductivity κ and absolute temperature T, promptly
。Because optimizing one of them physical parameter usually can be to the influence of another parameter counterproductive, so cause the maximization of ZT to be subjected to great challenge, in the past 50 years, people just bring up to the value of parameter Z T more than 1.
Summary of the invention
Goal of the invention of the present invention aims to provide electroless deposition nickel technology on a kind of silicon nanowires and based on the thermoelectric (al) power device of this technology, to remedy the technological gap on this field.
Purpose of the present invention can realize by technical scheme once:
Electroless deposition nickel technology on a kind of silicon nanowires, preparation process is:
1) based on the galvanic corrosion silicon nanowire array making processes of MEMS technology
(a) P type silicon (the about 0.05 Ω cm of resistivity) substrate cuts into 1.5cm * 1cm specification, according to standard RAC program cleaning silicon chip;
(b) at 35mM AgNO
3With etching in the mixing solutions after the 20%HF excusing from death, obtain SiNWs (silicon nanowires) array.
The SEM picture of its SiNWs has shown among the figure that prepared silicon nanowire structure is neat shown in Fig. 1 a, Fig. 1 b and Fig. 1 c, porosity is even, the about 100 μ m of nanowire height, and the about 50-150nm of diameter has than big L/D ratio.
2) dark porous silicon adopts electrochemical etching
(a) 40%HF mixes with the dehydrated alcohol volume ratio at 1: 0.8, adopts 40 under-20 ℃ respectively, 80mA/cm
2Current density is every 30s one-period etching 2h;
(b) the porous silicon 2 minutes post bakes of 600 ℃ of following short annealings in the RTA system after carving well utilize electron beam evaporation at the anode of porous silicon surface evaporation metal aluminium film as the thermoelectric (al) power device then.
This porous silicon microcosmic structure is shown in Fig. 2 a and Fig. 2 b.The about 5 μ m in its aperture, dark 250 μ m have than high aspect ratio.Thermal insulation properties is preferably arranged.
3) silicon nanowires electroless nickel deposition
(a) at first with silicon nanowires pre-treatment 1min in treating compound, put into electroless plating liquid then and under 80 ℃ of water-baths, react 30min.
(b) with the silicon nanowires of Ni plated with 80 ℃ of left and right sides washed with de-ionized water, 130 ℃ of oven dry down, 350 ℃ of rapid thermal annealing 30s in the RTA system then obtain the silicon nanowire array of nickel film.
The composition of described electroless plating liquid and proportioning: the nickel source is NiSO
46H
2O 0.1mol, buffer reagent are (NH
4)
2SO
40.05mol reductive agent is NH
4F 0.25mol, clamping together agent is Trisodium Citrate Sodium citrate 0.02mol.Load weighted medicine is put into beaker 100ml deionized water ultrasonic dissolution 30min.
The pH value of described electroless plating liquid is 8.5-9.5, regulates by splashing into strong aqua (28%).
Described treating compound is sodium lauryl sulphate (Sodium dodecyl sulfate) solution, and its concentration is 10mg/L
The silicon nanowire array that has deposited the nickel film is seen Fig. 3 a, Fig. 3 b and Fig. 3 c; Can see that surface of silicon nanowires has been deposited the skim metallic nickel equably; The nickel of nanoscale-P type silicon contact has higher thermal electron emission ability for ohmic contact on this theory of ship structures;
The distribution situation of the nickel of silicon nanowires electroless nickel plating is seen Fig. 4 a, Fig. 4 b and Fig. 4 c, and this EDS can show that the deposition of silicon nanowire array metal nickel film reduces gradually in upper end, middle part, top, bottom by spectrogram.
Thermoelectric (al) power device based on the nisiloy nano composite structure of above-mentioned technology preparation, from top to bottom be followed successively by: nickel dam, silicon nanowires layer, body silicon layer, porous silicon layer and aluminium coat, wherein nickel dam is that heat zone, aluminium coat are cryosphere, be respectively equipped with an electrode at nickel dam and aluminium coat, its structural models as shown in Figure 5.The Ni-SiNWS structural plane is because the quantum effect of nanoscale and big specific surface area and the length-to-diameter ratio of nano wire, stronger again surfactivity behind the nickel thin layer nanometer, this structure has good thermal electron emission ability, the assumed temperature gradient is reduced to the aluminium coat face by this surface, then thermoelectron at first enters body silicon by this structural plane place, enter dark porous silicon layer (this structure has lower thermal conductivity) then, then cross aluminium silicon Schotty potential barrier (raising thermoelectromotive force) and enter aluminium coat, acting is circulated back to the high temperature surface again to external circuit at last.
The output rating of this thermoelectric (al) power device and device temperature difference relation are seen Fig. 6, and this test result shows that the present invention has higher thermoelectric (al) power output, has huge potential using value.
This thermo-electric device principal character is:
1, manufacture craft of the present invention and MEMS process compatible mainly adopt electrochemical etching method, and cost is low, and is simple to operate, realize easily.Mainly be synthetic silicon nanowire array under room temperature on the body silicon materials, the about 30 μ m of its nano wire center line average, the about 40nm of mean diameter; This measure has reduced the thermal conductivity and the temperature diffusivity of material, has strengthened the quantum size effect of silicon nanowires, has improved the thermal electron emission ability;
2, pass through electroless nickel plating deposition techniques nano level nickel film on silicon nanowires, this moment, nickel and silicon formed good Ohmic contact, had further strengthened thermoelectric emissive power, had reduced the internal resistance of this thermoelectric structure; Electroless plating liquid is without phosphorus prescription, reduces thermoelectric emission efficiency thereby avoided phosphorus and nickel to form alloy.
3, dark porous silicon about the another side etching 200 μ m of silicon chip, and at its surperficial AM aluminum metallization film, this structure is owing to have bigger specific surface area and depth-to-width ratio, further increase the heat insulating ability of material, produce the thermoelectromotive force that Schottky barrier has increased this thermoelectric structure at aluminium silicon contact surface simultaneously.
Description of drawings
Fig. 1 a, Fig. 1 b and Fig. 1 c are followed successively by top view, side-view and the longitdinal cross-section diagram of SEM photo of the silicon nanowires of making of the present invention;
Fig. 2 a and Fig. 2 b are followed successively by the thermoelectric (al) power device back of the body dark porous silicon SEM in end photo top view and sectional view;
It is top view, side-view and the longitdinal cross-section diagram of the SEM photo behind the silicon nanowire array electroless nickel plating among the present invention that Fig. 3 a, Fig. 3 b and Fig. 3 c are followed successively by;
Fig. 4 a, Fig. 4 b and Fig. 4 c are followed successively by behind the silicon nanowire array electroless nickel plating nickel in the EDAX results at silicon nanowires top, bottom and middle part;
Fig. 5 is a thermoelectric (al) power device architecture synoptic diagram;
Fig. 6 is a thermoelectric (al) power device power output and temperature difference relation;
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with accompanying drawing and specific embodiment.
1, electroless deposition nickel technology on the silicon nanowires
1) based on the galvanic corrosion silicon nanowire array making processes of MEMS technology
(a) P type silicon (the about 0.05 Ω cm of resistivity) substrate cuts into 1.5cm * 1cm specification, according to standard RAC program cleaning silicon chip;
(b) at 30mM AgNO
3With etching 30min in the mixing solutions after the 20%HF excusing from death, obtain SiNWs (silicon nanowires) array.
2) dark porous silicon adopts electrochemical etching
(a) 40%HF mixes with the dehydrated alcohol volume ratio at 1: 0.8, adopts 40 under-20 ℃ respectively, 80mA/cm
2Current density is every 30s one-period etching 2h;
(b) carve porous silicon after good 2 minutes post bakes of short annealing under 600 ℃ of argon shields in the RTA system, utilize electron beam evaporation then at the anode of porous silicon surface evaporation metal aluminium film as the thermoelectric (al) power device.
3) silicon nanowires electroless nickel deposition
(a) be pre-treatment 1min in the sodium lauryl sulphate of 10mg/L with silicon nanowires in concentration at first, putting into the pH value then is that 8.5 electroless plating liquid react 30min (the pH value is regulated by 28% strong aqua) under 80 ℃ of water-baths.
(b) with the silicon nanowires of Ni plated with 80 ℃ of left and right sides washed with de-ionized water, 130 ℃ of oven dry down, then in the RTA system in 350 ℃ of following rapid thermal annealing 30s, obtain the silicon nanowire array of nickel film.
Embodiment 2
1) based on the galvanic corrosion silicon nanowire array making processes of MEMS technology
(a) P type silicon (the about 0.05 Ω cm of resistivity) substrate cuts into 1.5cm * 1cm specification, according to standard RAC program cleaning silicon chip;
(b) at 35mMAgNO
3With etching 40min in the mixing solutions after the 20%HF excusing from death, obtain SiNWs (silicon nanowires) array.
2) dark porous silicon adopts electrochemical etching
(a) 40%HF mixes with the dehydrated alcohol volume ratio at 1: 0.8, adopts 80mA/cm respectively under-20 ℃
2Current density etching 1h;
(b) carve porous silicon after good 2 minutes post bakes of short annealing under 600 ℃ of argon shields in the RTA system, utilize electron beam evaporation then at the anode of porous silicon surface evaporation metal aluminium film as the thermoelectric (al) power device.
3) silicon nanowires electroless nickel deposition
(a) be pre-treatment 1min in the sodium lauryl sulphate of 10mg/L with silicon nanowires in concentration at first, putting into the pH value then is that 9.5 electroless plating liquid react 30min under 80 ℃ of water-baths.
(b) with the silicon nanowires of Ni plated with 80 ℃ of left and right sides washed with de-ionized water, 130 ℃ of oven dry down, 350 ℃ of rapid thermal annealing 30s in the RTA system then obtain the silicon nanowire array of nickel film.
Embodiment 3
1) based on the galvanic corrosion silicon nanowire array making processes of MEMS technology
(a) P type silicon (the about 0.05 Ω cm of resistivity) substrate cuts into 1.5cm * 1cm specification, according to standard RAC program cleaning silicon chip;
(b) at 35mMAgNO
3With etching 40min in the mixing solutions of 20%HF, obtain SiNWs (silicon nanowires) array.
2) dark porous silicon adopts electrochemical etching
(a) 40%HF mixes with the dehydrated alcohol volume ratio at 1: 0.8, adopts 40 under-20 ℃ respectively, 80mA/cm
2Current density is every 30s one-period etching 2h;
(b) carve the 600 ℃ of following short annealings 2 minutes in the RTA system of porous silicon after good, utilize electron beam evaporation then at the anode of porous silicon surface evaporation metal aluminium film as the thermoelectric (al) power device.
3) silicon nanowires electroless nickel deposition
(a) be pre-treatment 1min in the sodium lauryl sulphate of 10mg/L with silicon nanowires in concentration at first, putting into the pH value then is that 9.0 electroless plating liquid react 30min under 80 ℃ of water-baths.
(b) with the silicon nanowires of Ni plated with 80 ℃ of left and right sides washed with de-ionized water, 130 ℃ of oven dry down, 350 ℃ of rapid thermal annealing 30s in the RTA system then obtain the silicon nanowire array of nickel film.、
In the step 1), the SEM picture of the silicon nanowires that obtains (SiNWs) array has shown among the figure that prepared silicon nanowire structure is neat shown in Fig. 1 a, Fig. 1 b and Fig. 1 c, porosity is even, the about 100 μ m of nanowire height, the about 50-150nm of diameter has than big L/D ratio.
Step 2) the porous silicon microcosmic structure that obtains is shown in Fig. 2 a and Fig. 2 b.The about 5 μ m in its aperture, dark 250 μ m have than high aspect ratio.Thermal insulation properties is preferably arranged
Step 3) has deposited the silicon nanowire array of nickel film and has seen Fig. 3 a, Fig. 3 b and Fig. 3 c; Can see that surface of silicon nanowires has been deposited the skim metallic nickel equably; The nickel of nanoscale-P type silicon contact has higher thermal electron emission ability for ohmic contact on this theory of ship structures;
The distribution situation of the nickel of silicon nanowires electroless nickel plating is seen Fig. 4 a, Fig. 4 b and Fig. 4 c, and this EDS can show that the deposition of silicon nanowire array metal nickel film reduces gradually in upper end, middle part, top, bottom by spectrogram.
2, based on the thermoelectric (al) power device of the nisiloy nano composite structure of above-mentioned technology preparation
The structural models of thermoelectric (al) power device as shown in Figure 5, thermoelectric (al) power device based on the nisiloy nano composite structure of above-mentioned technology preparation, from top to bottom be followed successively by: nickel dam, silicon nanowires layer, body silicon layer, porous silicon layer and aluminium coat, wherein nickel dam is that heat zone, aluminium coat are cryosphere, is respectively equipped with an electrode at nickel dam and aluminium coat.
As seen from Figure 5: the Ni-SiNWS structural plane is because the quantum effect of nanoscale and big specific surface area and the length-to-diameter ratio of nano wire, stronger again surfactivity behind the nickel thin layer nanometer, this structure has good thermal electron emission ability, the assumed temperature gradient is reduced to the aluminium coat face by this surface, then thermoelectron at first enters body silicon by this structural plane place, enter dark porous silicon layer (this structure has lower thermal conductivity) then, then cross aluminium silicon Schotty potential barrier (raising thermoelectromotive force) and enter aluminium coat, acting is circulated back to the high temperature surface again to external circuit at last.
The output rating of this thermoelectric (al) power device and device temperature difference relation are seen Fig. 6, and this test result shows that the present invention has higher thermoelectric (al) power output, has huge potential using value.
Claims (5)
1. electroless deposition nickel technology on the silicon nanowires, preparation process is:
1) based on the galvanic corrosion silicon nanowire array making processes of MEMS technology
(a) resistivity is the P type silicon substrate of 0.05 Ω cm, cuts into 1.5cm * 1cm specification, according to standard RAC program cleaning silicon chip;
(b) at the AgNO of 35mM
3With etching in the mixing solutions of 20%HF, obtain silicon nanowire array;
2) dark porous silicon adopts electrochemical etching
(a) 40%HF mixes with the dehydrated alcohol volume ratio at 1: 0.8, adopts 40 under-20 ℃ respectively, 80mA/cm
2Current density is every 30s one-period etching 2h;
(b) carve the 600 ℃ of following short annealings 2 minutes in the RTA system of porous silicon after good, utilize electron beam evaporation then at the anode of porous silicon surface evaporation metal aluminium film as the thermoelectric (al) power device;
3) silicon nanowires electroless nickel deposition
(a) at first with silicon nanowires pre-treatment 1min in treating compound, put into electroless plating liquid then and under 80 ℃ of water-baths, react 30min;
(b) with the silicon nanowires of Ni plated with 80 ℃ of left and right sides washed with de-ionized water, 130 ℃ of oven dry down, 350 ℃ of rapid thermal annealing 30s in the RTA system then obtain the silicon nanowire array of nickel film.
2. electroless deposition nickel technology on a kind of silicon nanowires according to claim 1, it is characterized in that: the composition of described electroless plating liquid and proportioning are: nickeliferous source NiSO in the 100ml deionized water
46H
2O 0.1mol, buffer reagent (NH
4)
2SO
40.05mol, reductive agent NH
4F 0.25mol clamps together agent Trisodium Citrate Sodium citrate 0.02mol.
3. electroless deposition nickel technology on a kind of silicon nanowires according to claim 1 is characterized in that: the pH value of described electroless plating liquid is 8.5-9.5, regulates by splashing into 28% strong aqua.
4. electroless deposition nickel technology on a kind of silicon nanowires according to claim 1 is characterized in that: described treating compound is a sodium dodecyl sulfate solution, and its concentration is 10mg/L.
5. based on the thermoelectric (al) power device of the nisiloy nano composite structure of claim 1 technology preparation, it is characterized in that: from top to bottom be followed successively by: nickel dam, silicon nanowires layer, body silicon layer, porous silicon layer and aluminium coat, wherein nickel dam is that heat zone, aluminium coat are cryosphere, is respectively equipped with an electrode at nickel dam and aluminium coat.
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| CN103151424B (en) * | 2013-03-12 | 2015-12-02 | 电子科技大学 | A kind of improvement chemical plating process prepares the method for metal electrode at porous silicon surface |
| CN103205808B (en) * | 2013-04-12 | 2016-05-25 | 西北工业大学 | A kind of preparation method of Spindt type cathode array |
| CN103205809B (en) * | 2013-04-12 | 2016-04-06 | 西北工业大学 | One prepares Si base TaSi 2the method of Nano pointed cone array |
| CN107099294A (en) * | 2017-04-11 | 2017-08-29 | 枣庄学院 | A kind of corrosive liquid and its application process for being used to prepare silicon nanowire structure |
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