CN102347223A - 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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- CN102347223A CN102347223A CN2011102986702A CN201110298670A CN102347223A CN 102347223 A CN102347223 A CN 102347223A CN 2011102986702 A CN2011102986702 A CN 2011102986702A CN 201110298670 A CN201110298670 A CN 201110298670A CN 102347223 A CN102347223 A CN 102347223A
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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 of coming in the silicon chip surface film forming through the colloidal state nano silicon particles.
Background technology
At present, semi-conductor industry develops rapidly, and doping is a crucial step in the semiconductor preparing process flow process.For example, have only 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 semiconductor doping has crucial meaning.
Modal semiconductor doping method is that diffusion and ion inject in the industry.For example, for most widely used semiconductor silicon, can utilize diffusion method in P type silicon chip, to mix 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 through the liquid phosphorus acyl chlorides, through discharging the furnace tubing of silicon chip arranged after sneaking into a spot 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 this 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, like BCl
3, B
2H
6Liquid source is like BBr
3, contain the spin coating liquid of boron element; Solid State Source, like BN, or the like.But various diffuse sources all 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.The ion injection 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 receives the bombardment of injecting ion in the doping process; Lattice sustains damage, and for recovering damage, ion need be heat-treated silicon chip after injecting.The drawback of ion implantation is a complex equipments, costs an arm and a leg, and 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, belong to diffusion method and mix through the colloidal state nano silicon particles.
A kind of colloidal state nano silicon particles that utilizes may further comprise the steps the method that silicon chip mixes:
Silicon nanoparticle surface to mixing is modified, and the surface is dispersed in the solvent through the silicon grain of modifying, and makes the colloidal state nano silicon particles; Make the colloidal state nano silicon particles remove film forming on the pretreated silicon chip through decontamination and oxide layer, after Overheating Treatment, form doped layer on the nearly surface of silicon chip on the surface.
Wherein, The silicon nanoparticle of said doping is Powdered; Can be through the preparation of various art methods, 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 almost has no defective.But for some silicon atom on 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%.
, be dissolved in them certain solvent and obtain solution and often can make its more convenient application 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, earlier 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 of the modification of organic molecule chain the 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 is carrying out containing carbon-carbon double bond or carbon carbon triple bond before the 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 let the silicon grain of tunicle parcel be scattered in solvent well, 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 accomplish finishing silicon grain.For example, the silicon grain of oxide-film is arranged, can select for use silane coupler to carry out coupling reaction for the surface.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 modifying the hydrophilic silicon grain in back, solvent is selected water for use for the surface.For the silicon grain through oleophylic after the finishing, solvent can be selected single organic solvent for use, also the mixture of several kinds of organic solvents.Wherein, to consider its stability, volatility and dissolubility when selecting organic solvent, the solvent of being selected for use on the one hand can not with described silicon grain generation chemical reaction, certain stability arranged; The volatility of the solvent of being selected for use on the other hand can not be very good, and in addition, the polarity of described organic solvent is close with the polarity of the lip-deep modification group of silicon grain, helps the dispersion of silicon grain like this.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 for use, phenmethylol; Terpinol; Chloroform, n-hexane, ethanol.
In the said 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 pass through preliminary treatment to said colloidal state nano silicon particles on silicon chip, and to remove the contamination and the oxide layer on surface, preprocess method is: silicon chip is put into hydrofluoric acid soak 1-60 second, with deionized water and absolute ethyl alcohol flushing, dry up then.
Make the colloidal state nano silicon particles remove 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 for use has (drop casting), spin coating (spin coating), dip-coating (dip coating), spraying (spray coating) inkjet printing (ink-jet printing), silk screen printing (screen printing) or the spool printing modes such as (roll-to-roll printing) to spool that is coated with of dripping.
Said colloidal state nano silicon particles is after film forming on the silicon chip is accomplished, and solvent can not volatilize fully, need solvent be dried through 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 high more diffusion that helps foreign atom more of heat treatment temperature, the temperature of generally selecting for use feeds oxygen-containing gas (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, use absolute ethyl alcohol and washed with de-ionized water then, dry up.
Beneficial effect of the present invention is mainly reflected in: the content of element silicon in the earth's crust is very big 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
Specify the present invention below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to this.
Embodiment 1
In the plasma preparation system of silicon grain, obtain the surface by the silicon grain of mixing phosphorus of 18 nanometers of hydrogen passivation, the standard deviation of the distribution of sizes of silicon grain is 9% of an 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 dispersion as far as possible of phosphorus silicon grain.In shear rate is 2000r/min, and reaction temperature is under 70 ℃ the situation, adds mass percent and be 25% silane coupler CH
2=C (CH
3) COO (CH
2)
3Si (OCH
3)
3, about pH value to 4, react and obtain the surface after 3 hours and mix the phosphorus silicon grain through what modify with the oxalic acid solution regulation system.From mixed liquor, separate through the phosphorus silicon grain of modifying of mixing the surface through centrifugation, 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, washes with deionized water and absolute ethyl alcohol successively then, dries up with hair dryer.Then the above-mentioned colloidal state nano silicon particles that makes is printed on silicon chip surface through dripping the mode that is coated with, makes the colloidal state nano silicon particles form thickness and be about 500 microns continuous film.Place Muffle furnace to silicon chip,, 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 in 350 ℃ of down insulations 30 minutes
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 uses absolute ethyl alcohol and washed with de-ionized water then, dries up, and detects with the silicon chip air cooling.With carrier concentration in the spreading resistance commercial measurement sample, the data that obtain are shown in accompanying drawing 2.Shown in accompanying drawing 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
In the plasma preparation system of silicon grain, obtain the surface by the silicon grain of mixing phosphorus of 44 nanometers of hydrogen passivation, the standard deviation of the distribution of sizes of silicon grain is 15% of an 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, become limpid, thereby obtain the silicon grain of surface through modifying until mixed liquor.From mixed liquor, separate through the phosphorus silicon grain of modifying of mixing the surface through centrifugation, 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, washes with deionized water and absolute ethyl alcohol successively then, dries up with hair dryer.Then the mode of the above-mentioned colloidal state nano silicon particles that makes through 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.Place Muffle furnace to silicon chip,, 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 in 220 ℃ of down insulations 15 minutes
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 uses absolute ethyl alcohol and washed with de-ionized water then, dries up, and detects with the silicon chip air cooling.With carrier concentration in the spreading resistance commercial measurement sample, the data that obtain are shown in accompanying drawing 3.Shown in accompanying drawing 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
In the plasma preparation system of silicon grain, obtain the surface by the silicon grain of mixing phosphorus of 7 nanometers of hydrogen passivation, the standard deviation of the distribution of sizes of silicon grain is 18% of an average-size, and the atomic percent of phosphorus doping is 16.6% in the silicon grain.Mixing the mixed liquor (trimethylbenzene is 20: 1 with the volume ratio of positive octadecylene) that the phosphorus silicon grain places trimethylbenzene and positive octadecylene; Under 250 ℃ temperature, carry out hydrosilylation reactions; Become limpid until mixed liquor, thereby obtain the silicon grain that then there is the organic molecule chain of 18 carbon on the surface.From mixed liquor, separate through the phosphorus silicon grain of modifying of mixing the surface through centrifugation, 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, washes with deionized water and absolute ethyl alcohol successively then, dries up with hair dryer.Then the above-mentioned colloidal state nano silicon particles that makes is printed on silicon chip surface through the mode that sprays, makes the colloidal state nano silicon particles form thickness and be about 300 microns continuous film.Place Muffle furnace to silicon chip,, 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 in 300 ℃ of down insulations 30 minutes
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 uses absolute ethyl alcohol and washed with de-ionized water then, dries up, and detects with the silicon chip air cooling.With carrier concentration in the spreading resistance commercial measurement sample, the data that obtain are shown in accompanying drawing 4.Shown in accompanying drawing 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
In the plasma preparation system of silicon grain, obtain the surface by the silicon grain of mixing phosphorus of 12 nanometers of hydrogen passivation, the standard deviation of the distribution of sizes of silicon grain is 10% of an 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 dispersion as far as possible of phosphorus silicon grain.In shear rate is 1500r/min, and reaction temperature is under 70 ℃ the situation, adds mass percent and be 25% silane coupler CH
2=CH (CH
2)
3Si (OC
2H
5)
3, about pH value to 4, react and obtain the surface after 5 hours and mix the phosphorus silicon grain through what modify with the oxalic acid solution regulation system.From mixed liquor, separate through the phosphorus silicon grain of modifying of mixing the surface through centrifugation, again it is scattered in the terpinol, mix the mass fraction (wt) of phosphorus silicon grain, be mixed with three kinds of different colloidal state nano silicon particles through change.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, washes with deionized water and absolute ethyl alcohol successively then, dries up with hair dryer.Then the mode of above-mentioned three kinds of colloidal state nano silicon particles that make through silk screen printing is printed on substrate surface respectively, makes to form thickness and be about 1000 microns continuous film, obtain sample 41, sample 42 and sample 43.Place Muffle furnace to three samples,, 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 in 300 ℃ of down insulations 40 minutes
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 uses absolute ethyl alcohol and washed with de-ionized water then, dries up, and detects with the silicon chip air cooling.Measure carrier concentration in each sample respectively with the spreading resistance technology, the data that obtain are shown in accompanying drawing 5.Shown in accompanying drawing 5, sample 41 is 10 with the carrier concentration on sample 42 surfaces
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
In the plasma preparation system of silicon grain, obtain the surface by the silicon grain of mixing phosphorus of 33 nanometers of hydrogen passivation, the standard deviation of the distribution of sizes of silicon grain is 14% of an average-size, and the atomic percent of phosphorus doping is 2% in the silicon grain.Mixing the mixed liquor (trimethylbenzene is 10: 7 with the volume ratio of positive laurylene) that the phosphorus silicon grain places trimethylbenzene and positive laurylene; Under 220 ℃ temperature, carry out hydrosilylation reactions; Become limpid until mixed liquor, thus obtain the surface be connected to 12 carbon the organic molecule chain mix the phosphorus silicon grain.From mixed liquor, separate through the phosphorus silicon grain of modifying of mixing the surface through centrifugation, 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, washes with deionized water and absolute ethyl alcohol successively then, dries up with hair dryer.Then the mode of the above-mentioned colloidal state nano silicon particles that makes through silk screen printing is printed on the silicon chip surface respectively, makes the colloidal state nano silicon particles form thickness and be about 750 microns continuous film, obtain sample 51, sample 52 and sample 53.Place Muffle furnace to three samples,, then silicon chip is transferred in 870 ℃ the tube furnace logical nitrogen oxygen mixed gas in the tube furnace, N in the mist rapidly in 350 ℃ of down insulations 20 minutes
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 uses absolute ethyl alcohol and washed with de-ionized water then, 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 carrier concentration in each sample respectively with the spreading resistance technology, the data that obtain are shown in accompanying drawing 6.Shown in accompanying drawing 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
In the plasma preparation system of silicon grain, obtain the surface by the silicon grain of mixing phosphorus of 5 nanometers of hydrogen passivation, the standard deviation of the distribution of sizes of silicon grain is 20% of an 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, become limpid, be connected to polyacrylic silicon grain thereby obtain the surface until mixed liquor.From mixed liquor, separate through the phosphorus silicon grain of modifying of mixing the surface through centrifugation, 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, washes with deionized water and absolute ethyl alcohol successively then, dries up with hair dryer.Then the mode of the above-mentioned colloidal state nano silicon particles that makes through silk screen printing is printed on the silicon chip surface respectively, makes the colloidal state nano silicon particles form thickness and be about 800 microns continuous film, obtain sample 61, sample 62 and sample 63.Place Muffle furnace to three samples,, then silicon chip is transferred in 1000 ℃ the tube furnace logical nitrogen oxygen mixed gas in the tube furnace, N in the mist rapidly in 300 ℃ of down insulations 45 minutes
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 uses absolute ethyl alcohol and washed with de-ionized water then, 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 carrier concentration in each sample respectively with the spreading resistance technology, the data that obtain are shown in accompanying drawing 7.Shown in accompanying drawing 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 (10)
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:
Silicon nanoparticle surface to mixing is modified, and the surface is dispersed in the solvent through the silicon grain of modifying, and makes the colloidal state nano silicon particles;
Make the colloidal state nano silicon particles remove film forming on the pretreated silicon chip through decontamination and oxide layer on the surface; Under 200-500 ℃ heat treatment 5-60 minute first earlier; At 750-1100 ℃, under oxygen-containing atmosphere heat treatment 30-120 minute once more, form doped layer subsequently on the nearly surface of silicon chip.
2. the method for claim 1 is characterized in that, said silicon nanoparticle is in advance by the silicon grain of hydrogen passivation, and its average-size is the 1-50 nanometer.
3. according to claim 1 or claim 2 method is characterized in that in the silicon nanoparticle of said doping, doped chemical is boron, aluminium, gallium, nitrogen, phosphorus or arsenic, and the atom percentage concentration of said doped chemical is 0.1%-20%.
4. according to claim 1 or claim 2 method; It is characterized in that the method that the silicon nanoparticle surface of mixing is modified is: under the environment of anaerobic, with being carried out hydrosilylation reactions by the silicon grain of hydrogen passivation and modifier in advance; Make the silicon grain of surface through modifying; Wherein, said modifier contains carbon-carbon double bond or carbon carbon triple bond, and an end of said modifier is the group of hydrophilic or oleophylic.
5. method as claimed in claim 4 is characterized in that, said modifier is positive laurylene, positive octadecylene or acrylic acid.
6. according to claim 1 or claim 2 method; It is characterized in that; The method that the silicon nanoparticle surface of mixing is modified is: will made its surface form oxide-film by the silicon grain oxidation of hydrogen passivation in advance; Utilize silane coupler to carry out coupling reaction again, make the surface of oxide-film connect the group of hydrophilic or oleophylic, make the silicon grain of surface through modifying.
7. method as claimed in claim 6 is characterized in that, said 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
8. according to claim 1 or claim 2 method is characterized in that, the surface is 0.1-80% through the weight percent concentration of the silicon grain modified in the said colloidal state nano silicon particles.
9. according to claim 1 or claim 2 method 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.
10. according to claim 1 or claim 2 method is characterized in that, after heat treatment once more, silicon chip is put into hydrofluoric acid soak 5-100 and clean second, uses absolute ethyl alcohol and washed with de-ionized water then, dries up.
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| CN103224238A (en) * | 2013-05-23 | 2013-07-31 | 刘国钧 | Preparation method of nano silicon composite material |
| CN103311511A (en) * | 2013-05-23 | 2013-09-18 | 刘国钧 | Preparation method of nanometer silicon composite material with core-shell structure |
| CN109983586A (en) * | 2016-11-03 | 2019-07-05 | 道达尔销售服务公司 | The surface treatment of solar battery |
| CN111624460A (en) * | 2020-06-28 | 2020-09-04 | 西安奕斯伟硅片技术有限公司 | Method for detecting defect distribution area of monocrystalline silicon |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003188393A (en) * | 2001-12-18 | 2003-07-04 | Sharp Corp | Manufacturing method for solar cell |
| JP2004221149A (en) * | 2003-01-10 | 2004-08-05 | Hitachi Ltd | Manufacturing method of solar cell |
| CN101814555A (en) * | 2010-04-12 | 2010-08-25 | 浙江大学 | Method for improving efficiency of solar cell |
| CN102047389A (en) * | 2008-04-25 | 2011-05-04 | 英诺瓦莱特公司 | Junction formation on wafer substrates using group IV nanoparticles |
-
2011
- 2011-09-30 CN CN 201110298670 patent/CN102347223B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003188393A (en) * | 2001-12-18 | 2003-07-04 | Sharp Corp | Manufacturing method for solar cell |
| JP2004221149A (en) * | 2003-01-10 | 2004-08-05 | Hitachi Ltd | Manufacturing method of solar cell |
| CN102047389A (en) * | 2008-04-25 | 2011-05-04 | 英诺瓦莱特公司 | Junction formation on wafer substrates using group IV nanoparticles |
| CN101814555A (en) * | 2010-04-12 | 2010-08-25 | 浙江大学 | Method for improving efficiency of solar cell |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224238A (en) * | 2013-05-23 | 2013-07-31 | 刘国钧 | Preparation method of nano silicon composite material |
| CN103311511A (en) * | 2013-05-23 | 2013-09-18 | 刘国钧 | Preparation method of nanometer silicon composite material with core-shell structure |
| CN103311511B (en) * | 2013-05-23 | 2015-05-27 | 刘国钧 | Preparation method of nanometer silicon composite material with core-shell structure |
| CN109983586A (en) * | 2016-11-03 | 2019-07-05 | 道达尔销售服务公司 | The surface treatment of solar battery |
| CN109983586B (en) * | 2016-11-03 | 2024-03-12 | 道达尔销售服务公司 | Surface treatment of solar cells |
| CN111624460A (en) * | 2020-06-28 | 2020-09-04 | 西安奕斯伟硅片技术有限公司 | Method for detecting defect distribution area of monocrystalline silicon |
| CN111624460B (en) * | 2020-06-28 | 2022-10-21 | 西安奕斯伟材料科技有限公司 | Method for detecting defect distribution area of monocrystalline silicon |
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