CN102347223B - Method for doping silicon wafer with colloidal silicon nano particles - Google Patents
Method for doping silicon wafer with colloidal silicon nano particles Download PDFInfo
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- CN102347223B CN102347223B CN 201110298670 CN201110298670A CN102347223B CN 102347223 B CN102347223 B CN 102347223B CN 201110298670 CN201110298670 CN 201110298670 CN 201110298670 A CN201110298670 A CN 201110298670A CN 102347223 B CN102347223 B CN 102347223B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 148
- 239000010703 silicon Substances 0.000 title claims abstract description 147
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
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- 230000003588 decontaminative effect Effects 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract 2
- 238000007254 oxidation reaction Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- 239000011574 phosphorus Substances 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 238000002161 passivation Methods 0.000 claims description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 9
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- -1 octadecylene Chemical group 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 4
- 238000004064 recycling Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011856 silicon-based particle Substances 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 10
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 6
- 125000004437 phosphorous atom Chemical group 0.000 description 6
- 238000003892 spreading Methods 0.000 description 6
- 230000007480 spreading Effects 0.000 description 6
- 238000006701 autoxidation reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
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- 238000007650 screen-printing Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
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- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 2
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- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for doping a silicon wafer with colloidal silicon nano particles. The method comprises the following steps of: modifying surface of doping nano silicon particles, and dispersing the silicon particles with the modified surface in a solvent to manufacture colloidal silicon nano particles; and forming a film of the colloidal silicon nano particles on a silicon wafer which is subjected to pretreatments of decontamination and removal of an oxidation layer, carrying out heat treatment firstly at a temperature of 200-500 DGE C for 5-60 minutes, carrying out heat treatment in an oxygen atmosphere at a temperature of 750-1100 DEG C for 30-120 minutes again, and forming a doping layer on the near surface of the silicon wafer. Silicon element in raw materials selected in the invention is rich in the earth crust, obtained easily and non-toxic. In addition, by applying the colloidal silicon nano particles, the doping process of the silicon wafer is simplified and the doping in selective regions can be simply and conveniently realized.
Description
Technical field
The present invention relates to field of photovoltaic materials, relate in particular to a kind of method that silicon chip is mixed come in the silicon chip surface film forming by the colloidal state nano silicon particles.
Background technology
At present, semi-conductor industry develops rapidly, and doping is a step very important in the semiconductor preparing process flow process.For example, only have P type and N-type impurity are mixed semiconductor, just can obtain the semiconductor of P type and N-type, just can obtain PN junction.And PN junction is the key structure of transistor, integrated circuit of a lot of semiconductor device such as solar cell, junction type etc.So the semiconductor doping tool is of great significance.
Industrial modal semiconductor doping method is diffusion and Implantation.For example, for most widely used semiconductor silicon, can utilize diffusion method to mix in the P type silicon chip to mix boron in phosphorus or the N-type silicon chip to form PN junction.The most frequently used phosphorous diffusion source is liquid phosphorus acyl chlorides (POCl
3).When mixing, carrier gas is by the liquid phosphorus acyl chlorides, by discharging the furnace tubing of silicon chip arranged after sneaking into a small amount of oxygen, thereby makes silicon chip surface generate phosphorous oxide layer, and the phosphorus in the oxide layer is heated and diffuses to silicon chip inside.The drawback of the method is that phosphoryl chloride phosphorus oxychloride is poisonous, and is not easy to carry out the constituency diffusion.Boron diffusion source commonly used has gaseous source, such as BCl
3, B
2H
6Liquid source is such as BBr
3, contain the spin coating liquid of boron element; Solid Source, such as BN, etc.But various diffuse sources have its shortcoming, all have strong toxicity and corrosivity such as gaseous state diffuse source and liquid state diffusion source commonly used, and solid-state diffusion source BN uses simply, safety, but moisture absorption is very fast, and can cause the deposition of impurity.Implantation is to utilize the ion beam bombardment silicon chip of high energy impurity to be mixed such as phosphorus or boron to realize mixing, because silicon chip is subject to the bombardment of ion in the doping process, lattice sustains damage, and for recovering damage, needs behind the Implantation silicon chip is heat-treated.The drawback of ion implantation is that equipment is complicated, and expensive, production efficiency is lower.
Summary of the invention
The invention provides a kind of method of utilizing the colloidal state nano silicon particles that silicon chip is mixed, come silicon chip is mixed in the silicon chip surface film forming by the colloidal state nano silicon particles, belong to diffusion method and mix.
A kind of colloidal state nano silicon particles that utilizes may further comprise the steps the method that silicon chip mixes:
The silicon nanoparticle surface of mixing is modified, the surface is dispersed in the solvent through the silicon grain of modifying, make the colloidal state nano silicon particles; Make the colloidal state nano silicon particles remove film forming on the pretreated silicon chip on the surface through decontamination and oxide layer, after Overheating Treatment, form doped layer on the nearly surface of silicon chip.
Wherein, the silicon nanoparticle of described doping is Powdered, can be by various art methods preparations, for example silane plasma decomposes (specifically can referring to be the method for putting down in writing in the Chinese invention patent of ZL200910098051.1 in the patent No.) and thermal decomposition of silane also can be utilized commercially available.Because the silicon grain volume is very little, so silicon grain inside is almost without any defective.But for some silicon atom on the silicon grain surface, be not its all key all by saturated, therefore, preferred among the present invention what adopt is in advance by the silicon grain of hydrogen passivation, its average-size is the 1-50 nanometer.
Doped chemical is III or V major element in the silicon nanoparticle of described doping, as: boron, aluminium, gallium, nitrogen, phosphorus, arsenic etc., the atom percentage concentration of doped chemical is 0.1%-20%.
, they are dissolved in certain solvent and obtain solution often can make its application convenient by the silicon nanoparticle of pulverous doping of hydrogen passivation in advance.The present invention is called the colloidal state nano silicon particles to resulting solution.
Can to be dispersed in well in the solvent by the silicon nanoparticle of the doping of hydrogen passivation in order making in advance, first hydrophily or lipophile modification to be carried out in the surface of silicon grain:
Under the environment of anaerobic, carry out hydrosilylation reactions in the system that carries out hydrosilylation reactions with being transferred to by the silicon grain of hydrogen passivation in advance, thereby realize that the organic molecule chain is to the modification on silicon grain surface.One end of organic molecule chain connects silicon grain, and the other end is hydrophilic or the group of oleophylic.Wherein, the organic molecule chain contained carbon-carbon double bond or carbon carbon triple bond before carrying out hydrosilylation reactions, and for example they can be alkene or alkynes; Preferably positive laurylene, positive octadecylene and acrylic acid.
In air, understood autoxidation by the doped silicon particle of hydrogen passivation in advance, thereby form oxide-film on its surface; Perhaps, also can be under controlled condition, specially at silicon grain superficial growth oxide-film.In order to allow the silicon grain of tunicle parcel be scattered in well solvent, can select suitable method to connect the group of hydrophilic or oleophylic on the surface of film according to the character of film, and then finish the finishing to silicon grain.For example, for the surface silicon grain of oxide-film is arranged, can select silane coupler to carry out coupling reaction.Silane coupler is Y (CH
2)
nSiX
3, wherein Y represents organo-functional group, and X represents hydrolyzable group, and the value of n is 0,1,2 or 3, CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3Or CH
2=CH (CH
2)
3Si (OC
2H
5)
3It is preferred silane coupler.
When preparation colloidal state nano silicon particles, through hydrophilic silicon grain after modifying, solvent is selected water for the surface.For the silicon grain through oleophylic after the finishing, solvent can be selected single organic solvent, also the mixture of several organic solvents.Wherein, to consider its stability, volatility and dissolubility when selecting organic solvent, on the one hand selected solvent can not with described silicon grain generation chemical reaction, certain stability be arranged; The volatility of selected solvent can not be very good on the other hand, and in addition, the polarity of described organic solvent is close with the polarity of the lip-deep modification group of silicon grain, is conducive to like this dispersion of silicon grain.Can be selected from alkane, alcohol, aldehyde, ketone, carboxylic acid, ester, amine, organosiloxane, aromatic compound or halogen-containing hydrocarbon etc. according to above principle organic solvent of the present invention, generally can select toluene, phenmethylol, terpinol, chloroform, n-hexane, ethanol.
In the described colloidal state nano silicon particles, the surface is 0.1-80% through the weight percent concentration of the silicon grain of modification.
Before the film forming, silicon chip need to pass through preliminary treatment to described colloidal state nano silicon particles on silicon chip, and to remove contamination and the oxide layer on surface, preprocess method is: silicon chip is put into hydrofluoric acid soak 1-60 second, then with deionized water and absolute ethyl alcohol flushing, dry up.
So that the colloidal state nano silicon particles is removed film forming on the pretreated silicon chip on the surface through above-mentioned decontamination and oxide layer, the thin film-forming method that can select has to drip and is coated with (drop casting), spin coating (spin coating), dip-coating (dip coating), spraying (spray coating) inkjet printing (ink-jet printing), silk screen printing (screen printing) or spool to the modes such as printing (roll-to-roll printing) of spool.
Described colloidal state nano silicon particles is after film forming is finished on the silicon chip; solvent can not volatilize fully; need to solvent be dried by heat treatment; at this moment; the heat treatment atmosphere that do not need protection, temperature is 200-500 ℃, heat treatment time is 5-60 minute; stay through the nano silicon particles of surface through the doping of modification, forming thickness at silicon chip surface is the continuous film of 0.01-1500 micron.
When the nano silicon particles that mixes after the silicon chip surface film forming, it is carried out further heat treatment, the foreign atom in the doped silicon nanometer particle film is diffused in the silicon chip.At this moment, the more high diffusion that more is conducive to foreign atom of heat treatment temperature, the temperature of generally selecting passes into oxygen-containing gas (preferred nitrogen and oxygen) at 750-1100 ℃ in diffusion furnace in heat treatment process, and the time of processing is 30-120 minute.
After twice heat treatment, silicon chip is put into hydrofluoric acid immersion 5-100 cleans second,, the colloidal state nano silicon particles is removed, then use absolute ethyl alcohol and washed with de-ionized water, dry up.
Beneficial effect of the present invention is mainly reflected in: the content of element silicon in the earth's crust is very large in the selected raw material, is easy to get, nontoxic.Simultaneously, the application of colloidal state nano silicon particles makes the work simplification that silicon chip is mixed, and mixes in realization constituency that can be easy.
Description of drawings
Fig. 1 is the process chart that utilizes the colloidal state nano silicon particles that silicon chip is mixed;
Fig. 2 is the carrier concentration profile figure of sample among the embodiment 1;
Fig. 3 is the carrier concentration profile figure of sample among the embodiment 2;
Fig. 4 is the carrier concentration profile figure of sample among the embodiment 3;
Fig. 5 is the carrier concentration profile figure of sample among the embodiment 4;
Fig. 6 is the carrier concentration profile figure of sample among the embodiment 5;
Fig. 7 is the carrier concentration profile figure of sample among the embodiment 6.
Embodiment
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to this.
Obtain the surface by the silicon grain of mixing phosphorus of 18 nanometers of hydrogen passivation in the plasma preparation system of silicon grain, the standard deviation of the distribution of sizes of silicon grain is 9% of average-size, and the atomic percent of phosphorus doping is 5% in the silicon grain.Place air mixing the phosphorus silicon grain, at room temperature their autoxidations.After 60 days, there has been the phosphorus silicon grain of mixing of oxide-film to put into the mixed solution of second alcohol and water (volume ratio of second alcohol and water is 5: 2) on the surface at autoxidation, utilized the emulsification pretreatment machine to make and mix the as far as possible dispersion of phosphorus silicon grain.Be 2000r/min in shear rate, reaction temperature is in 70 ℃ the situation, adds mass percent and be 25% silane coupler CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3, about the pH value to 4 with the oxalic acid solution regulation system, react obtain after 3 hours the surface through modification mix the phosphorus silicon grain.By centrifugation the surface is separated from mixed liquor through the phosphorus silicon grain of mixing of modifying, again it is scattered in the n-hexane, obtain the colloidal state nano silicon particles.The concentration of silicon grain is 17% (wt) in the colloidal state nano silicon particles of gained.The N-type of 1.5 centimetres of 1.5 cm x undoped, and to put into concentration expressed in percentage by volume be that 5% hydrofluoric acid soaked 1 minute to silicon chip, and then successively with deionized water and absolute ethyl alcohol flushing, electricity consumption dries up.Then the above-mentioned colloidal state nano silicon particles that makes is printed on silicon chip surface by dripping the mode that is coated with, makes the colloidal state nano silicon particles form thickness and be about 500 microns continuous film.Silicon chip is placed Muffle furnace, in 350 ℃ of lower insulations 30 minutes, then silicon chip is transferred to rapidly in 870 ℃ the tube furnace, be incubated 1 hour, lead to nitrogen oxygen mixed gas, N in the mist in the tube furnace
2: O
2=7: 1.After heat treatment finished, to room temperature, it was that 5% hydrofluoric acid soaked 60 seconds that silicon chip is put into concentration expressed in percentage by volume, and residual silicon grain is removed, and then uses absolute ethyl alcohol and washed with de-ionized water, dries up, and detects with the silicon chip air cooling.With carrier concentration in the spreading resistance commercial measurement sample, the data that obtain as shown in Figure 2.As shown in Figure 2, the carrier concentration of sample surfaces is 10
15The order of magnitude, the carrier concentration of sample interior are 10
12The order of magnitude.This phenomenon explanation, sample carrier concentration before doping is 10
12The order of magnitude, after the doping of colloidal state nano silicon particles, the phosphorus atoms in the colloidal state nano silicon particles has been diffused in the sample, and the carrier concentration of sample surfaces brings up to 10
15The order of magnitude has formed doped layer on the nearly surface of sample.Therefore we can utilize the colloidal state nano silicon particles that silicon chip is mixed.
Embodiment 2
Obtain the surface by the silicon grain of mixing phosphorus of 44 nanometers of hydrogen passivation in the plasma preparation system of silicon grain, the standard deviation of the distribution of sizes of silicon grain is 15% of average-size, and the atomic percent of phosphorus doping is 8% in the silicon grain.Place ethanol and acrylic acid mixed liquor (ethanol and acrylic acid volume ratio are 3: 1) mixing the phosphorus silicon grain, under ultraviolet irradiation, carry out hydrosilylation reactions, until mixed liquor becomes limpid, thereby obtain the silicon grain of surface through modifying.By centrifugation the surface is separated from mixed liquor through the phosphorus silicon grain of mixing of modifying, again it is scattered in the ethanol, obtain the colloidal state nano silicon particles.The concentration of silicon grain is 20% (wt) in the colloidal state nano silicon particles of gained.The N-type of 1.5 centimetres of 1.5 cm x undoped, and to put into concentration expressed in percentage by volume be that 5% hydrofluoric acid soaked 30 seconds to silicon chip, and then successively with deionized water and absolute ethyl alcohol flushing, electricity consumption dries up.Then the mode of the above-mentioned colloidal state nano silicon particles that makes by spin coating is printed on silicon chip surface, makes the colloidal state nano silicon particles form thickness and be about 0.7 micron continuous film.Silicon chip is placed Muffle furnace, in 220 ℃ of lower insulations 15 minutes, then silicon chip is transferred to rapidly in 870 ℃ the tube furnace, be incubated 45 minutes, lead to nitrogen oxygen mixed gas, N in the mist in the tube furnace
2: O
2=7: 1.After heat treatment finished, to room temperature, it was that 5% hydrofluoric acid soaked 30 seconds that silicon chip is put into concentration expressed in percentage by volume, and residual silicon grain is removed, and then uses absolute ethyl alcohol and washed with de-ionized water, dries up, and detects with the silicon chip air cooling.With carrier concentration in the spreading resistance commercial measurement sample, the data that obtain as shown in Figure 3.As shown in Figure 3, the carrier concentration of sample surfaces is 10
14The order of magnitude, the carrier concentration of sample interior are 10
12The order of magnitude.This phenomenon explanation, sample carrier concentration before doping is 10
12The order of magnitude, after the doping of colloidal state nano silicon particles, the phosphorus atoms in the colloidal state nano silicon particles has been diffused in the sample, and the carrier concentration of sample surfaces brings up to 10
14The order of magnitude has formed doped layer on the nearly surface of sample.Therefore we can utilize the colloidal state nano silicon particles that silicon chip is mixed.
Embodiment 3
Obtain the surface by the silicon grain of mixing phosphorus of 7 nanometers of hydrogen passivation in the plasma preparation system of silicon grain, the standard deviation of the distribution of sizes of silicon grain is 18% of average-size, and the atomic percent of phosphorus doping is 16.6% in the silicon grain.The mixed liquor (volume ratio of trimethylbenzene and positive octadecylene is 20: 1) of mixing the phosphorus silicon grain and place trimethylbenzene and positive octadecylene, under 250 ℃ temperature, carry out hydrosilylation reactions, until mixed liquor becomes limpid, thereby obtain the silicon grain that then there is the organic molecule chain of 18 carbon on the surface.By centrifugation the surface is separated from mixed liquor through the phosphorus silicon grain of mixing of modifying, again it is scattered in the toluene, obtain the colloidal state nano silicon particles.The concentration of silicon grain is 8% (wt) in the colloidal state nano silicon particles of gained.The N-type of 1.5 centimetres of 1.5 cm x undoped, and to put into concentration expressed in percentage by volume be that 5% hydrofluoric acid soaked 20 seconds to silicon chip, and then successively with deionized water and absolute ethyl alcohol flushing, electricity consumption dries up.Then the above-mentioned colloidal state nano silicon particles that makes is printed on silicon chip surface by the mode that sprays, makes the colloidal state nano silicon particles form thickness and be about 300 microns continuous film.Silicon chip is placed Muffle furnace, in 300 ℃ of lower insulations 30 minutes, then silicon chip is transferred to rapidly in 870 ℃ the tube furnace, be incubated 1.5 hours, lead to nitrogen oxygen mixed gas, N in the mist in the tube furnace
2: O
2=7: 1.After heat treatment finished, to room temperature, it was that 5% hydrofluoric acid soaked 10 seconds that silicon chip is put into concentration expressed in percentage by volume, and residual silicon grain is removed, and then uses absolute ethyl alcohol and washed with de-ionized water, dries up, and detects with the silicon chip air cooling.With carrier concentration in the spreading resistance commercial measurement sample, the data that obtain as shown in Figure 4.As shown in Figure 4, the carrier concentration of sample surfaces is 10
15The order of magnitude, the carrier concentration of sample interior are 10
12The order of magnitude.This phenomenon explanation, sample carrier concentration before doping is 10
12The order of magnitude, after the doping of colloidal state nano silicon particles, the phosphorus atoms in the colloidal state nano silicon particles has been diffused in the sample, and the carrier concentration of sample surfaces brings up to 10
15The order of magnitude has formed doped layer on the nearly surface of sample.Therefore we can utilize the colloidal state nano silicon particles that silicon chip is mixed.
Embodiment 4
Obtain the surface by the silicon grain of mixing phosphorus of 12 nanometers of hydrogen passivation in the plasma preparation system of silicon grain, the standard deviation of the distribution of sizes of silicon grain is 10% of average-size, and the atomic percent of phosphorus doping is 9.7% in the silicon grain.Place air mixing the phosphorus silicon grain, at room temperature their autoxidations.After 30 days, there has been the phosphorus silicon grain of mixing of oxide-film to put into the mixed solution of second alcohol and water (volume ratio of second alcohol and water is 5: 2) on the surface at autoxidation, utilized the emulsification pretreatment machine to make and mix the as far as possible dispersion of phosphorus silicon grain.Be 1500r/min in shear rate, reaction temperature is in 70 ℃ the situation, adds mass percent and be 25% silane coupler CH
2=CH (CH
2)
3Si (OC
2H
5)
3, about the pH value to 4 with the oxalic acid solution regulation system, react obtain after 5 hours the surface through modification mix the phosphorus silicon grain.By centrifugation the surface is separated from mixed liquor through the phosphorus silicon grain of mixing of modifying, again it is scattered in the terpinol, mix the mass fraction (wt) of phosphorus silicon grain by change, be mixed with three kinds of different colloidal state nano silicon particles.No. 1 granule density is that 30% (wt), No. 2 granule densities are that 50% (wt), No. 3 granule densities are 70% (wt).The N-type of 1.5 centimetres of three 1.5 cm x of taking from same silicon chip undoped, and to put into concentration expressed in percentage by volume be that 5% hydrofluoric acid soaked 60 seconds to the silicon chip substrate, and then successively with deionized water and absolute ethyl alcohol flushing, electricity consumption dries up.Then the mode of above-mentioned three kinds of colloidal state nano silicon particles that make by silk screen printing is printed on respectively substrate surface, makes to form thickness and be about 1000 microns continuous film, obtain sample 41, sample 42 and sample 43.Three samples are placed Muffle furnace, in 300 ℃ of lower insulations 40 minutes, then silicon chip is transferred to rapidly in 1000 ℃ the tube furnace, be incubated 1 hour, lead to nitrogen oxygen mixed gas, N in the mist in the tube furnace
2: O
2=7: 1.After heat treatment finished, to room temperature, it was that 5% hydrofluoric acid soaked 60 seconds that silicon chip is put into concentration expressed in percentage by volume, and residual silicon grain is removed, and then uses absolute ethyl alcohol and washed with de-ionized water, dries up, and detects with the silicon chip air cooling.Measure respectively carrier concentration in each sample with the spreading resistance technology, the data that obtain as shown in Figure 5.As shown in Figure 5, the carrier concentration on sample 41 and sample 42 surfaces is 10
15The order of magnitude, the carrier concentration on sample 43 surfaces is 10
16The order of magnitude, the carrier concentration of three sample interior all are starkly lower than the carrier concentration on surface.This phenomenon explanation, after the doping of colloidal state nano silicon particles, the phosphorus atoms in the colloidal state nano silicon particles has been diffused in the sample, and the carrier concentration of sample surfaces brings up to 10
15Perhaps 10
16The order of magnitude has formed doped layer on the nearly surface of sample.Therefore we can utilize the colloidal state nano silicon particles that silicon chip is mixed.
Embodiment 5
Obtain the surface by the silicon grain of mixing phosphorus of 33 nanometers of hydrogen passivation in the plasma preparation system of silicon grain, the standard deviation of the distribution of sizes of silicon grain is 14% of average-size, and the atomic percent of phosphorus doping is 2% in the silicon grain.The mixed liquor (volume ratio of trimethylbenzene and positive laurylene is 10: 7) of mixing the phosphorus silicon grain and place trimethylbenzene and positive laurylene, under 220 ℃ temperature, carry out hydrosilylation reactions, until mixed liquor becomes limpid, thus obtain the surface be connected to 12 carbon the organic molecule chain mix the phosphorus silicon grain.By centrifugation the surface is separated from mixed liquor through the phosphorus silicon grain of mixing of modifying, again it is scattered in the chloroform, obtain the colloidal state nano silicon particles.The concentration of silicon grain is 50% (wt) in the colloidal state nano silicon particles of gained.The N-type of 1.5 centimetres of three 1.5 cm x of taking from same silicon chip undoped, and to put into concentration expressed in percentage by volume be that 5% hydrofluoric acid soaked 10 seconds to the silicon chip substrate, and then successively with deionized water and absolute ethyl alcohol flushing, electricity consumption dries up.Then the mode of the above-mentioned colloidal state nano silicon particles that makes by silk screen printing is printed on respectively the silicon chip surface, makes the colloidal state nano silicon particles form thickness and be about 750 microns continuous film, obtain sample 51, sample 52 and sample 53.Three samples are placed Muffle furnace, in 350 ℃ of lower insulations 20 minutes, then silicon chip is transferred to rapidly in 870 ℃ the tube furnace logical nitrogen oxygen mixed gas in the tube furnace, N in the mist
2: O
2=7: 1.Be incubated after 1 hour, take out sample 51; Be incubated after 1.5 hours, take out sample 52; Be incubated after 2 hours, take out sample 53.After heat treatment finished, to room temperature, it was that 5% hydrofluoric acid soaked 10 seconds that silicon chip is put into concentration expressed in percentage by volume, and residual silicon grain is removed, and then uses absolute ethyl alcohol and washed with de-ionized water, dries up, and detects with the silicon chip air cooling.The square resistance of three samples is respectively: sample 51,3.49K Ω/; Sample 52,1.95K Ω/; Sample 53,1.29K Ω/.Measure respectively carrier concentration in each sample with the spreading resistance technology, the data that obtain as shown in Figure 6.As shown in Figure 6, the carrier concentration of three sample surfaces all is 10
15The order of magnitude, the carrier concentration of three sample interior all are starkly lower than the carrier concentration on surface.This phenomenon explanation, after the doping of colloidal state nano silicon particles, the phosphorus atoms in the colloidal state nano silicon particles has been diffused in the sample, and the carrier concentration of sample surfaces brings up to 10
15The order of magnitude has formed doped layer on the nearly surface of sample.Therefore we can utilize the colloidal state nano silicon particles that silicon chip is mixed.
Embodiment 6
Obtain the surface by the silicon grain of mixing phosphorus of 5 nanometers of hydrogen passivation in the plasma preparation system of silicon grain, the standard deviation of the distribution of sizes of silicon grain is 20% of average-size, and the atomic percent of phosphorus doping is 16% in the silicon grain.Place ethanol and acrylic acid mixed liquor (ethanol and acrylic acid volume ratio are 3: 1) mixing the phosphorus silicon grain, under ultraviolet irradiation, carry out hydrosilylation reactions, until mixed liquor becomes limpid, be connected to polyacrylic silicon grain thereby obtain the surface.By centrifugation the surface is separated from mixed liquor through the phosphorus silicon grain of mixing of modifying, again it is scattered in the acetone, obtain the colloidal state nano silicon particles.The concentration of silicon grain is 45% (wt) in the colloidal state nano silicon particles of gained.The N-type of 1.5 centimetres of three 1.5 cm x of taking from same silicon chip undoped, and to put into concentration expressed in percentage by volume be that 5% hydrofluoric acid soaked 50 seconds to the silicon chip substrate, and then successively with deionized water and absolute ethyl alcohol flushing, electricity consumption dries up.Then the mode of the above-mentioned colloidal state nano silicon particles that makes by silk screen printing is printed on respectively the silicon chip surface, makes the colloidal state nano silicon particles form thickness and be about 800 microns continuous film, obtain sample 61, sample 62 and sample 63.Three samples are placed Muffle furnace, in 300 ℃ of lower insulations 45 minutes, then silicon chip is transferred to rapidly in 1000 ℃ the tube furnace logical nitrogen oxygen mixed gas in the tube furnace, N in the mist
2: O
2=7: 1.Be incubated after 1 hour, take out sample 61; Be incubated after 1.5 hours, take out sample 62; Be incubated after 2 hours, take out sample 63.After heat treatment finished, to room temperature, it was that 5% hydrofluoric acid soaked 10 seconds that silicon chip is put into concentration expressed in percentage by volume, and residual silicon grain is removed, and then uses absolute ethyl alcohol and washed with de-ionized water, dries up, and detects with the silicon chip air cooling.The square resistance of three samples is respectively: sample 61,1.11K Ω/; Sample 62,642.0 Ω/; Sample 63,411.5 Ω/.Measure respectively carrier concentration in each sample with the spreading resistance technology, the data that obtain as shown in Figure 7.As shown in Figure 7, the carrier concentration of three sample surfaces is 10
16The order of magnitude, the carrier concentration of three sample interior all are starkly lower than the carrier concentration on surface.This phenomenon explanation, after the doping of colloidal state nano silicon particles, the phosphorus atoms in the colloidal state nano silicon particles has been diffused in the sample, and the carrier concentration of sample surfaces brings up to 10
16The order of magnitude has formed doped layer on the nearly surface of sample.Therefore we can utilize the colloidal state nano silicon particles that silicon chip is mixed.
Claims (6)
1. one kind is utilized the colloidal state nano silicon particles to the method that silicon chip mixes, and it is characterized in that, may further comprise the steps:
The silicon nanoparticle surface of mixing is modified, the surface is dispersed in the solvent through the silicon grain of modifying, make the colloidal state nano silicon particles;
Described silicon nanoparticle is in advance by the silicon grain of hydrogen passivation, and its average-size is the 1-50 nanometer; In the silicon nanoparticle of described doping, doped chemical is boron, aluminium, gallium, nitrogen, phosphorus or arsenic, and the atom percentage concentration of described doped chemical is 0.1%-20%;
Make the colloidal state nano silicon particles remove film forming on the pretreated silicon chip on the surface through decontamination and oxide layer, under 200-500 ℃ heat treatment 5-60 minute first first, at 750-1100 ℃, under oxygen-containing atmosphere heat treatment 30-120 minute again, form doped layer on the nearly surface of silicon chip subsequently;
The surface is 0.1-80% through the weight percent concentration of the silicon grain of modification in the described colloidal state nano silicon particles; After heat treatment again, silicon chip is put into hydrofluoric acid soak 5-100 and clean second, then use absolute ethyl alcohol and washed with de-ionized water, dry up.
2. the method for claim 1, it is characterized in that, the method that the silicon nanoparticle surface of mixing is modified is: under the environment of anaerobic, to be carried out hydrosilylation reactions by the silicon grain of hydrogen passivation and modifier in advance, make the silicon grain of surface through modifying, wherein, described modifier contains carbon-carbon double bond or carbon carbon triple bond, and an end of described modifier is the group of hydrophilic or oleophylic.
3. method as claimed in claim 2 is characterized in that, described modifier is positive laurylene, positive octadecylene or acrylic acid.
4. the method for claim 1, it is characterized in that, the method that the silicon nanoparticle surface of mixing is modified is: will be made its surface form oxide-film by the silicon grain oxidation of hydrogen passivation in advance, the recycling silane coupler carries out coupling reaction, make the surface of oxide-film connect the group of hydrophilic or oleophylic, make the silicon grain of surface through modifying.
5. method as claimed in claim 4 is characterized in that, described silane coupler is CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3Or CH
2=CH (CH
2)
3Si (OC
2H
5)
3
6. the method for claim 1 is characterized in that, also comprises: described colloidal state nano silicon particles is when the silicon chip surface film forming, and forming thickness is the continuous film of 0.01-1500 micron.
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