CN102312291A - Doped casting monocrystalline silicon and preparation method - Google Patents
Doped casting monocrystalline silicon and preparation method Download PDFInfo
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- CN102312291A CN102312291A CN201010218718XA CN201010218718A CN102312291A CN 102312291 A CN102312291 A CN 102312291A CN 201010218718X A CN201010218718X A CN 201010218718XA CN 201010218718 A CN201010218718 A CN 201010218718A CN 102312291 A CN102312291 A CN 102312291A
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Abstract
The invention relates to a monocrystalline silicon material used in the semiconductor field, in particular to a continuous monocrystalline silicon solid entity material suitable for the photovoltaic field. A traditional Czochralski monocrystalline silicon material has lower tolerance on impurities comprising metal, oxygen, carbon and the like and heavily-doped III-family and V-family impurities in performance, and has various defects including a vortex defect and an oxygen stacking fault defect. The invention provides semiconductor casting monocrystalline silicon doped with the oxygen, the carbon, nitrogen and germanium and a production method thereof, wherein the semiconductor casting monocrystalline silicon does not have or basically does not have the vortex defect and the oxygen stacking fault defect, and moreover, the tolerance of the semiconductor casting monocrystalline silicon on the impurities comprising transition metal, the heavily-doped III-family and V-family impurities and the like is improved in semiconductor performance; and under the same impurity concentration, the semiconductor casting monocrystalline silicon has better photovoltaic semiconductor performance and the like.
Description
Technical field
The present invention relates generally to be used for the single crystal silicon material of semiconductor applications, be specially adapted to the continuous silicon single crystal solid solid material of photoelectric field.
Background technology
Should have most possibly based on the sensitive cell of crystal silicon (or claiming photovoltaic cell, solar cell) solar radiation power is converted into the efficient of electric current and permanent as far as possible work-ing life and rate of decay.This determines by multiple factor, the purity of silicon material for example, the type of silicon crystal (monocrystalline, polycrystalline) and defective, Impurity Distribution and crystal orientation, internal stress.Wherein, the silicon single crystal sensitive cell is considered to have the highest efficient.Simultaneously, use, tend to make the silicon crystal blank (entity) of large-size in the industry,, thereby obtain higher production efficiency with the wafer of acquisition large-size because silicon crystal is made into wafer; And the defective and the internal stress of reduction silicon crystal help to increase the wafer size that can produce, also help to improve the output capacity of finished product and non-defective unit.
Although will improve the semiconducting behavior of silicon crystal usually; Need highly purified as far as possible silicon raw material to come growing crystal; And reduce foreign matter content as far as possible, but absolute pure material is industrial non-existent, for example; For the silicon single crystal raw material with the method production of improvement west door that is widely used in the photovoltaic field, its metals content impurity is generally 5*10
15Cm
-3, and the photovoltaic that adopts some cost effective methods to produce is used the silicon raw material, oxygen, carbon, metal and other impurity are often up to 5*10
16Cm
-3More than.Thereby for the certain silicon raw material of purity, it is even more important how to improve its performance.Known in silicon crystal, comprise the suitable doping material, can improve the crystalline performance.For example, through mixing special impurity in raw material or in the crystal growing process, some performances of silicon crystal obtain to improve under some situation.For example, document CN01815935.4 proposes, and in FZ or CZ silicon single-crystal, mixes nitrogen, can reduce or eliminate oxygen and cause stacking fault defect, and CN200910099995.0 proposes, and the nitrogen of some amount mixes casting monocrystalline silicon, can improve the mechanical property of silicon single crystal.Crystal silicon mixes the germanium of some amount, it is generally acknowledged its mechanical property of raising, and helps to reduce the crystalline defective.On the other hand, such as impurity such as oxygen, carbon, heavy metals, be commonly considered as detrimental impurity in the crystal silicon, cause defective and the infringement of the infringement of semiconducting behavior, particularly its photoelectric properties, reduction as much as possible in the crystal silicon.And plurality of impurities is when existing jointly, because interaction to each other is too complicated, its influence to silicon crystal is clear far away.
Summary of the invention
Therefore; The purpose of this invention is to provide a kind of adulterated crystal silicon; Particularly mixed and be considered to the crystal silicon of deleterious oxygen, carbon impurity usually; Can not only avoid oxygen carbon impurity itself to the crystal silicon Effect on Performance, and can reduce harmful heavy metal the infringement of its semiconducting behavior, especially photoelectric properties and the performance of raising silicon crystal.
Particularly; The present invention proposes a kind of adulterated direction solidified cast silicon single crystal, comprise crystal ingot, wafer, including at it provides the III of its electrical property characteristic family or/and outside the V group element doping; Also containing distinctive impurity comprises: about (MV, down together) 0.2～4*10
17Cm
-3Carbon (atomicity unit, down with); About 0.1～12*10
16Cm
-3Nitrogen; About 0.5～20*10
17Cm
-3Oxygen, about 0.2*10
16～1*10
20Cm
-3Germanium.Described III, the V group element impurity that electrical characteristic are provided comprises for example boron, aluminium, gallium, indium, or phosphorus, arsenic, antimony etc. and equivalent impurity lithium for example, and they as the alms giver or led, make it demonstrate characteristic of semiconductor in crystal silicon.
The content of above-mentioned characteristic impurity of the present invention further is preferably nitrogenous about 1.5～4.5*10
15Cm
-3Further be preferably the about 0.5～2.5*10 of carbon containing
17Cm
-3And be preferably and contain the about 1～10*10 of oxygen
17Cm
-3Be preferably germanic about 1～50*10
16Cm
-3
Wherein, the preferred version of each impurity concentration scope can be independent of each other; Also can be corresponding, promptly higher a kind of impurity content, other corresponding higher impurity content; Perhaps lower a kind of impurity content, other corresponding lower foreign matter contents.For example, contain nitrogen 1.5～4.5*10
15Cm
-3, carbon 0.5～2.5*10
17Cm
-3, oxygen 1～10*10
17Cm
-3With germanium 1～50*10
16Cm
-3Casting monocrystalline silicon.
Among the present invention, ge content further is preferably 1～20*10
16Cm
-3Lower ge content can reduce the silicon single crystal cost when guaranteeing certain premium properties.Higher ge content, for example, germanic 2*10
20Cm
-3Or 6*10
20Cm
-3Crystal silicon, though expect that its mechanical property further improves, the raising that electrical property improves with respect to content is tending towards weakening, and cost is higher.
Doped with II I family element impurity in the silicon single crystal, like boron, gallium, aluminium, or the lithium of equivalence, form the p N-type semiconductorN; Doping V group element impurity forms the n N-type semiconductorN, is made generally in tabular crystal, i.e. p type or n type wafer.P type or n N-type semiconductorN are made part with n type or p type impurity again and are mixed, and form the crystal or the wafer that comprise p-n junction, and crystal or wafer can be made semiconducter device thus, like diode, thyristor, sensitive cell.
About the doping in the silicon crystal, except causing III that electroconductibility changes, V group element, also have many other impurity and possible (initiatively) impurity.Because the complicacy between the impurity, between impurity and the SiGe interacts, and the influence of crystal growth different condition and make photronic complex process by crystal silicon; Usually; Be difficult to the influence that produces from each single doping impurity, dope the performance change of crystal silicon after the plurality of impurities acting in conjunction, and can only be by means of the direct viewing of test sample performance; Be aided with rational analysis, just can provide definite conclusion.The applicant finds under study for action, adopts quartz crucible, comprises quartz ceramic crucible; When making direction solidified cast silicon single crystal, if the crucible inwall scribbles nitrogenous disengaging coating, and/or in raw material fusing back and process of setting; Provide such as suitable nitrogenous sources such as nitrogen atmosphere, if the adulterated silicon raw material of P type or N type is doped with the germanium of trace, the casting monocrystalline silicon that then obtains; The casting monocrystalline silicon that more not germanic same silicon material is made has longer minority carrier life time, better detrimental impurity (for example heavy metal) tolerance; And the contriver finds, thereafter in the crystal of manufacturing semiconductor element, wafer or the battery sheet process; Suitable thermal treatment, for example annealing, it shows better intrinsic gettering effect.The sensitive cell of processing aspect minority carrier life time and radiation resistance, has more excellent performance.The contriver has analyzed the crystal silicon of the doping trace germanium with above-mentioned outstanding representation, finds to have such characteristic: it includes average 0.2～4*10
17Cm
-3Carbon, 0.1～12*10
16Cm
-3Nitrogen, 0.5～20*10
17Cm
-3Oxygen and 0.2*10
16～1*10
20Cm
-3Germanium.Wherein the contriver finds, mixes when existing at carbon, nitrogen, oxygen, and germanium is low to moderate 0.2*10
16Cm
-3Just demonstrate minority carrier life time and detrimental impurity tolerance, radiation-resistant advantage, at 0.2*10
16Cm
-3～100*10
16Cm
-3When increasing germanium in the scope, crystalline dislocation, minority carrier life time, radiation-resistant advantage increase with the increase of germanium; Germanium further increases, up to 1*10
20/ cm
3, except above-mentioned aspect continued to improve, the crystalline machining property was also progressively improved thereupon.The applicant finds, the advantage of above-mentioned germanic adulterated crystal silicon, and the content with oxygen, nitrogen, carbon interrelates again, for example for the adulterated crystal silicon that is substantially free of oxygen and nitrogen, above-mentioned one or multinomially mix reduction with the obvious advantage or the disappearance that germanium brings.The applicant further finds, if in the P type mixes leading silicon raw material, contain a spot of phosphorus, at about 0.5～5*10
16Cm
-3Scope in; For example; From the silicon material (referring to another application case CN200910053361.1 of the applicant) that the metalluragical silicon direct purification obtains, comprise minority carrier life time, some photoelectric properties of the tolerance of silicon material detrimental impurity are further improved, and improve with the raising of phosphorus content.The applicant finds, the raising of above-mentioned performance is superior to the summation of the performance raising that doping nitrogen independent in the existing knowledge, germanium, carbon, oxygen institute possibly cause.To this, after applicant's further investigation, description below is proposed: when adopting quartz crucible; The quartzy composition of crucible inwall at high temperature, gets in the silicon through thin disengaging coating; Cause oxygen to mix in the silicon thus, and part gaseous state silicon oxide compound is diffused into outside the crucible, the carbon in the graphite oxide well heater becomes CO; Together with or the CO gaseous diffusion that generates of the quartz crucible that has contact graphite heater oxidation and absorbed by silicon, cause carbon, oxygen to mix in the silicon; Simultaneously, the nitrogen in the nitrogenous coating of crucible inwall or the nitrogen of other nitrogenous sources also mix in the silicon.Oxygen, carbon, nitrogen solidify and subsequent cool down in and the germanium acting in conjunction, with detrimental impurity generation intrinsic gettering and trap reaction in the silicon material, wherein, nitrogen has promoted oxygen precipitation and impurity trap effect, thus, has improved the photoelectric properties of crystal silicon.And germanium is reducing dislocation and the lattice distortion that lattice dislocation, particularly displacement carbon cause; When adsorbing some impurity (chemically reactive of germanium is higher than silicon); Again can with oxygen, carbon, nitrogen generation complex interactions; Comprise lattice dislocation and distortion due to prevent oxygen and the oxygen trap, improve the absorption and the inactivation effect of impurity.The adding of phosphorus, compound and possible with p type impurity with the heavy metal bonded, be prone to form the defect center, thereby also can improve the intrinsic gettering effect, strengthen the tolerance of crystal silicon to detrimental impurity.Thus, the germanium of trace can be allowed higher oxygen level.Thereby under the condition that germanium exists, suitable high oxygen concn will be of value to the photoelectric properties of crystal silicon.The applicant finds that the oxygen doping content is at 3～20*10
17Cm
-3Scope in, along with the raising of oxygen concn, the photoelectric properties of crystal silicon improve the tolerance of detrimental impurity.This part has confirmed above-mentioned explanation.Also explain the wafer of processing is made appropriate heat treatment, will further improve the intrinsic gettering effect.Can reach a conclusion thus; Its semi-conductor of crystal silicon that the present invention is obtained in above-mentioned embodiment or the raising of photoelectric properties; Be not only to depend on method of manufacture, and depend on the concentration of above-mentioned oxygen, nitrogen, carbon, germanium, therefore; Expection is mixed above-mentioned each impurity through other method, also can obtain similar beneficial effect.Know by inference thus, to the silicon material of purifying, because before being purified to the typical 6N purity of photoelectricity level from metallurgical grade silicon; Normally need spend considerable cost with further reduction phosphorus content,, make the silicon material after crystallization, comprise an amount of oxygen, nitrogen, carbon, germanium if adopt method of the present invention; So; The phosphorus of trace need not be removed but and can obtain at least equally good photoelectric properties in the raw material, like this, has just obtained to practice thrift cost and the double dominant that improves performance.Similarly, adopt the present invention, part is used carbonaceous carbon head material, also can obtain to reduce cost to improve the effect of performance.
Though present scientific and technological level; The semi-conductor of the complicated interaction partners crystal silicon between alloying element that thoroughly discloses denier and different alloying element or the influence of photoelectric properties are far away; But bold judgement, expection and test that this can not stop people to carry out according to the rational faculty, and therefrom find to be of value to the processing of Technological Economy aspect.The good performance of above-mentioned doped polycrystal silicon on semi-conductor or photoelectric properties that the present invention finds although the mechanism of pointing out includes the composition of supposition, do not influence design of the present invention is used for industry to obtain beneficial effect.
Though direction solidified cast device based on quartz crucible that contains nitrogenous disengaging coating and graphite heater; Can provide the needed part at least of crystal silicon of the present invention carbon, nitrogen and oxygen to mix; The mode that other are suitable; As long as can offer an amount of said impurity of crystal silicon, also can select to be used for realizing the present invention.For example, for the carbon impurity, directly in raw material, add the material of carbon elements; Like silit, carbon dust, carbonate, or partly use carbon head material, or at fusing and solidificating period; The atmosphere of the material of carbon elements is provided,, also can realizes mixing of carbon like CO2, CO.On the other hand, adopt the silicon single crystal raw material that contains an amount of carbon, for example, the silicon single crystal raw material that uses metallurgy method or metallurgical chemistry method to purify also can be without carbon dope or few carbon dope.Mix for nitrogen, in raw material, add nitrogenous substances, for example silicon nitride also can substitute nitrogenous disengaging coating fully, for example when using the crucible of unazotized coating such as barium oxide or barium salt; Also can be through using nitrogenous crucible such as silicon nitride crucible or silicon nitride combined silicon carbide crucible.After the raw material fusing, nitrogen-containing atmosphere is provided, at least partly replaces with nitrogen, can realize the purpose of nitrating like inert gas argon with protectiveness.But had better not during changing silicon, use pure nitrogen gas atmosphere,, generate excessive silicon nitride deposition or scum silica frost easily, consume a large amount of silicon material, reduce material use efficiency though pure nitrogen gas atmosphere can realize that the saturated of nitrogen mixes during changing silicon.The upper limit 12*10 of nitrating scope provided by the invention
16Cm
-3With the about 4.5*10 of preferred itrogen content of getter with nitrogen doped range limit
15Cm
-3, respectively corresponding its saturated solid solubility and near saturated solid solubility concentration the fusing point thereof in silicon is through the distribution concentration of nitrogen after the fractional condensation in crystal silicon, far below near the saturated solid solubility 6～10*10 of the nitrogen silicon fusing point
18Cm
-3The applicant finds that in other impurity content ranges of the present invention, itrogen content of getter with nitrogen doped is high more, and the nitrating advantage that obtains basically is obvious more.Simultaneously, though leveling off under zero the crystalline growth velocity, the theoretical solid solubility of nitrogen is 4.5 (+/-1) * 10 in the crystal silicon
15Cm
-3But according to experimental observation, when crystalline growth velocity reached 2.5mm/min, the actual solid solubility of nitrogen had just reached 2 times of above-mentioned value; And under the Quench curing condition that uses laser, reach 5ms
-1Crystalline growth velocity the time, the solid solubility of nitrogen can be up to 10
20Cm
-3The nitrogen of saturated solid solubility when exceeding room temperature or fusing point will form the silicon nitride deposition in crystal, or nitrogen-complex body, or the accumulation of impurities center, and in impurity level of the present invention, these complex bodys and gathering center etc. will be of value to the crystalline performance.Nitrogen is in crystal silicon, and have two kinds of forms at least: displacement nitrogen and nitrogen are right.Usually infrared spectroscopy is detected only is that nitrogen in the silicon is to concentration.The diffusion of displacement nitrogen is very slow, but nitrogen is very fast to the velocity of diffusion in silicon, even this makes cooling or annealing stage after the crystal silicon growth is accomplished that nitrogen atmosphere is provided, still can obtain the effect that nitrogen impurity mixes crystal silicon.
The doping of oxygen also can be through providing the material that contains oxygen element in raw material, silica material for example, and carbonate, or use crucible that the material that contains oxygen element processes such as Natural manganese dioxide, zirconium white, lime crucible to wait and realize.The atmosphere that contains oxygen element is provided, for example aqueous atmosphere, or contain the atmosphere of SiO, can realize that also oxygen of the present invention mixes.
Oxygen, carbon and nitrogen are similar, can supersaturation in crystal silicon, and the saturation balance amount in the melt, carbon is 40*10
17Cm
-3Oxygen 2.75*10
18Cm
-3The oxygen and the carbon that exceed the saturated solid solubility of crystal can form deposition or scum silica frost, or the impurity deathnium, or leave crystal through diffusion.In doping content scope of the present invention, oxygen, carbon content are the performances that is of value to silicon crystal, yet, exceed the bigger quantity of above-mentioned scope, will cause the crystal property to affect adversely.
Realize method of mixing germanium of the present invention, except that can using the germanic silicon raw material of script, an amount of germanium of part by weight adding that also can before and after molten silicon, directly convert by atomic percent.For example, if will obtain average germanic 10*10
16Cm
-3Crystal silicon, for the silicon raw material of 1000kg, need mix the germanium grain of 5.2g before solidifying.
It is pointed out that impurity of the present invention, is not to be evenly distributed in the silicon crystal.Because impurity segregation phenomena will occur in solidifying; All impurity all will solidify the direction uneven distribution with particular concentration gradient mode edge according to segregation coefficient; And the complicacy between the impurity interacts, and has then formed the modulation of the concentration gradient distribution that this segregation is caused.Obviously, the performance of crystal silicon of the present invention is the influence that receives above-mentioned these non-uniform Distribution patterns of impurity, thereby also receives the influence of growing method.
The applicant also finds; Silicon single crystal that contains foregoing trace carbon, nitrogen, oxygen and germanium or silicon single crystal ingot that the above-mentioned family of III of the present invention or V group element have mixed in right amount; If further contain the hydrogen of sufficient quantity, its semi-conductor, photoelectricity and mechanical property further improve.Its mechanism comprises the electroactive of Hydrogen Energy passivation impurity and defective, form complex body with transition metal and make its passivation, and the complicacy of possible hydrogen and oxygen carbon nitrogen germanium and complex body thereof interacts.Hydrogen in the crystal silicon also can with shallow donor, shallow acceptor, deep energy level metallic impurity and other defect effect, form various complex bodys.These complex bodys are electroneutral mostly, therefore, mix the electroactive of Hydrogen Energy passivation impurity and defective in the silicon.Metallic impurity in the silicon are introduced deep energy level and are influenced performance such as its minority carrier life time, and Hydrogen Energy combines with metallic impurity, removal or change deep energy level.
Mix hydrogen and also the heavily doped silicon material of boron (photovoltaic silicon that is for example obtained by the metallurgical grade silicon purifying) is had additional benefits: hydrogen and boron form the HB complex body; Make that boron concentration reduces in the silicon; Resistivity raises; Not only influence basic semiconducting behavior, its passivation part of boron also can reduce the optical attenuation effect of heavily doped boron wafer, thereby improves the photronic photoelectric properties of being made by this type crystal silicon.Similarly, other donor impurities comprise that aluminium, gallium, indium etc. also can generate complex body with hydrogen and are passivated, and resistivity are risen and the performance of crystal silicon improves the tolerance of boron, aluminium, gallium, indium.On the other hand, hydrogen also combines with the alms giver, generates hydrogen-donor pair.Behind hydrogen plasma treatment phosphorous doped silicon crystal, the HP complex body generates, thus possible explanation hydrogen can increase the tolerance of crystal silicon in the present invention to donor impurity.
Make crystal silicon contain an example of the method for an amount of hydrogen; Be comprise that the silicon raw material melts, solidifies, optional link in the temperature-fall period provides hydrogenous atmosphere; Or aqueous atmosphere (comprising air atmosphere), comprise the atmosphere of low pressure and pressurization (greater than a normal atmosphere).The example of another kind method is that hydrogen ion injects.In addition, can introduce hydrogen during the wet chemical etching technique wafer, this is normally processing the after-applied processing of silicon wafer.
The doping sufficient quantity of hydrogen can be at the arbitrary value between the saturated solid solubility concentration of its saturated solid solubility concentration to 1/100, between preferred 0.1～0.5 times of saturated solid solubility.When the oxygen in the silicon material, when boron content is high; Because hydrogen and boron, hydrogen and oxygen can form complex body respectively; Adulterated hydrogen concentration can be higher, and according to oxygen, boron content difference, can be arranged between 0.01～30ppma; For example 0.02,0.08,0.2,0.3,0.5,0.6,0.7,0.8,1,1.3,1.5,1.7,2,2.5,3,4,5,5.5,6,7,8,9,10,15,20,25ppma, or the like.In addition, because hydrogen also can form complex body with phosphorus, therefore, be mixed with the crystal silicon of phosphorus, adulterated hydrogen richness also can be more higher.
Because between the uneven distribution and each impurity of impurity of the present invention in crystal silicon, exist complex interactions between impurity and other impurity, different monocrystalline silicon growing methods possibly form different impurities and distribute and the discrepant silicon single crystal of performance.For this reason, the present invention proposes the embodiment of several kinds of different methods making silicon single crystal of the present invention.A kind of is that embodiment is, uses the vertical direction coagulation system, in the directional freeze crucible, melt adulterated raw material after, make molten silicon begin upwards to solidify through the cooling crucible bottom as direction from the bottom, obtain silicon single crystal entity of the present invention.Another kind of embodiment is that employing seed crystal revulsion utilizes the specific orientation and the single crystal seed of rule to induce the growth of silicon single crystal, obtains silicon single crystal entity of the present invention.Wherein, Seed crystal revulsion embodiment preferred is, the bottom at the crucible of vertical direction coagulation system is provided with one or more single crystal seed of inducing crystal growth; Seed crystal can cover the mode of part crucible bottom at least with tiling, is placed in the bottom of common crucible; Also can be arranged on the seed crystal installation site place of the crucible that contains the seed crystal installation site, the seed crystal that is positioned at the crucible bottom extreme lower position that common described seed crystal installation site is a particular design holds cavity, then; Through the thermal field that provides vertical temperature gradient to distribute to crucible; At least in lower section solid-state, the top of melted silicon material and seed crystal is again through cooling off crucible bottom seed crystal position at the seed crystal that keeps crucible bottom; The molten silicon of cooling; Make molten silicon the solid-state melt on it of seed crystal begin at the interface upwards solidify gradually, until solidifying completion, promptly obtain the adulterated silicon single crystal entity of seed crystal inductive of the present invention.Another embodiment is to have the crucible at crystal selector position bottom using, wherein; The crystal selector position is positioned at the minimum position of crucible, adopts the vertical direction freezing method, and molten silicon is begun from the crystal selector position in crucible; Solidify as direction from top to bottom, can obtain complete silicon single crystal entity.When using seed crystal to make doped monocrystalline silicon of the present invention, preferably its doping composition and the identical or close seed crystal of target doped polycrystal silicon composition preferably use a little seed crystal of germanic slightly height.
Doped monocrystalline silicon of the present invention; Has the metallic impurity tolerance that good anti-metallic impurity, particularly transition metal impurity pollute; And good semi-conductor, photoelectricity and machining property, be suitable for manufacturing semiconductor element, semiconductor wafer, especially be suitable for the optoelectronic semiconductor wafer.For example; By the adulterated silicon single crystal entity of p type of the present invention; Along suitable direction cutting, form the brilliant unit or the wafer of suitable thickness, promptly obtain brilliant unit of p N-type semiconductorN or wafer; This crystalline substance unit or wafer can be made into the brilliant unit of the semiconductor element that comprises p-n junction or wafer and manufacturing semiconductor element or device, for example the brilliant unit of diode, the brilliant unit of thyristor, diode, thyristor, sensitive cell sheet or sensitive cell.For example, the part of the p type silicon wafer that the present invention is obtained is carried out phosphorus doping, and the phosphorus doping of the few partial depth of single face for example just obtains to comprise the silicon wafer of p-n junction.But silicon photoelectric cell slice is meant the silicon wafer that has p-n junction and conductive contact, can form the potential difference projected current through illumination at conductive contact; The sensitive cell sheet has just formed sensitive cell or has claimed photovoltaic cell through drawing conductor wire and be encapsulated in the suitable framework at conductive contact.
Brilliant unit of semiconductor element of the present invention or wafer; The semiconductor element that refers to directly to form, include at least one p-n junction and conductive contact (or line, band) by silicon single crystal of the present invention; These semiconductor elements just form semiconductor device through encapsulation, through electrical conductor other semiconductor elements of connection and auxiliary element.
The doped p type wafer that obtains further by photronic processes, is promptly obtained sensitive cell, and the battery that its more common silicon single crystal ingot is processed has high light energy use efficiency and work-ing life.
The invention provides a kind of sensitive cell thus, comprising: by the wafer that successive crystal silicon entity of the present invention forms, optional thermal treatment wafer; P-n junction in the wafer; The ARC of choosing wantonly on the wafer surface; Optional one deck at least from back surface field and passivation layer; And the conductive contact on the wafer; The conductor wire that the transparent glass of optional encapsulated wafer and backboard and the conductive contact from wafer are drawn.
Embodiment
Use the vertical direction freezing method, use the vertical direction coagulation system that has graphite heater and plumbago crucible holder cover, use inwall to scribble the quartz ceramic crucible that silicon nitride breaks away from coating, the silicon raw material that is used to mix germanium melts and direction is solidified.The thickness of adjustment crucible coating layer, atmosphere, air pressure and the gas flow rate of crucible during the processing links such as adjustment heat, melts, solidified, cooling, and the treatment time of above-mentioned each link of change can obtain nitrogen, carbon, oxygen, the different crystal ingot of ge content.Through using the crucible of different size, can obtain the silicon single crystal ingot of the present invention of various size.Through the doping different test consistent with this embodiment, obtainable part example be listed below (unlisted in other III that possibly contain, V group element, hydrogen and other impurity sample segment) (content unit is every cubic centimetre of atomicity) with crystal silicon composition of better photoelectric properties:
Appearance crystalline substance 1, carbon containing 0.2*10
17Nitrogen 1*10
16Oxygen 0.5*10
17, germanium 0.5*10
16
The brilliant 1a of appearance, carbon containing 0.3*10
17Nitrogen 0.5*10
16Oxygen 0.5*10
17, germanium 0.5*10
16
The brilliant 1b of appearance, carbon containing 0.4*10
17Nitrogen 0.8*10
16Oxygen 0.5*10
17, germanium 0.5*10
16
Appearance crystalline substance 2, carbon containing 0.25*10
17Nitrogen 5*10
16Oxygen 2*10
17, germanium 5*10
16
Appearance crystalline substance 3, carbon containing 0.5*10
17Nitrogen 6*10
16Oxygen 3*10
17, germanium 20*10
16
Appearance crystalline substance 4, carbon containing 0.25*10
17Nitrogen 12*10
16Oxygen 14*10
17, germanium 90*10
16
Appearance crystalline substance 5, carbon containing 3*10
17Nitrogen 10*10
16Oxygen 10*10
17, germanium 5*10
19
Appearance crystalline substance 6, carbon containing 3*10
17Nitrogen 5*10
16Oxygen 3*10
17, germanium 50*10
16
Appearance crystalline substance 7, carbon containing 4*10
17Nitrogen 8*10
16Oxygen 7*10
17, germanium 80*10
16
Appearance crystalline substance 8, carbon containing 0.5*10
17Nitrogen 2.5*10
16Oxygen 0.6*10
17, germanium 100*10
16, phosphorus 5*10
16
Appearance crystalline substance 9, carbon containing 0.4*10
17Nitrogen 1*10
16Oxygen 1.5*10
17, germanium 5*10
16, phosphorus 3*10
16
Appearance crystalline substance 10, carbon containing 1*10
17Nitrogen 8*10
16Oxygen 2.5*10
17, germanium 50*10
16, phosphorus 4*10
16
Appearance crystalline substance 11, carbon containing 0.5*10
17Nitrogen 2*10
16Oxygen 15*10
17, germanium 1*10
20, phosphorus＜0.1*10
16
The single crystal silicon semiconductor entity of other the p types consistent with the present invention and the example of wafer, its impurity average content be (wherein, electrically impurity is listed with relative concentration) as follows:
Appearance crystalline substance 12, carbon containing 1.8*10
17Nitrogen 3.3*10
16Oxygen 2*10
17, germanium 1*10
17, boracic 0.3ppma,
Appearance crystalline substance 13, carbon containing 3*10
17Nitrogen 5*10
16Oxygen 3*10
17, germanium 50*10
16, boracic 0.2ppma contains gallium 0.3ppma;
Appearance crystalline substance 14, carbon containing 0.8*10
17Nitrogen 0.8*10
16Oxygen 4*10
17, germanium 20*10
16, boracic 0.8ppma, phosphorous 0.3ppma;
Appearance crystalline substance 15, carbon containing 2*10
17Nitrogen 6*10
16Oxygen 15*10
17, germanium 15*10
16, boracic 0.3ppma contains the hydrogen of saturated solid solubility.
Through paired observation and test; Above-mentioned adulterated silicon single crystal and the wafer of processing thereof and battery sheet; Aspect the raising of the performance after metallic impurity tolerance, III, V family impurity tolerance, resistivity, microdefect density comprise dislocation desity, minority carrier lifetime, thermal treatment, the radiation resistance, aspect such as machining property; More do not contain the crystal silicon that the ad eundem silicon material same procedure of described impurity is processed, be significantly improved.
Silicon single crystal of the present invention, according to different clotting method described below, its monocrystalline ratio is difference to some extent; Best situation is to obtain 100% monocrystalline, secondly, can obtainablely be to comprise the crystal ingot that the minority on-monocrystalline is mingled with; For example, the monocrystalline ratio is between 51～99%.
Crystal silicon of the present invention; Preferred large-sized crystal ingot, under the same terms, it contains the monocrystalline of more ratios and less relatively crystal boundary; Not only production efficiency is high; And can be made into large-sized element or wafer, be more suitable in processing dynamical semiconducter device, for example diode, silicon controlled rectifier, sensitive cell sheet and sensitive cell.Through using large-sized crucible; Can obtain large-sized crystal ingot; For example; Have 2 sizes being at least about 25cm separately and the crystal ingot of the third direction size of 20cm at least on the edge with on the vertical horizontal section of crystal growth direction, perhaps have at least about the length of side of 50cm and the crystal ingot of the height of 25cm at least.By its wafer processed and battery sheet, correspondingly have 2 sizes at least about 25cm.
The dimensional data (cm) of some silicon single crystal crystal ingot embodiment of the present invention:
Long by 20, wide by 25, high by 25; Long by 28, wide by 28, high by 25; Long by 35, wide by 35, high by 27;
Long by 40, wide by 40, high by 26; Long by 45, wide by 45, high by 22; Long by 50, wide by 55, high by 27;
Long by 80, wide by 80, high by 35; Long by 100, wide by 100, high by 27; Long by 100, wide by 100, high by 38;
The dimensional data (cm) of some silicon single crystal wafers of the present invention, battery sheet embodiment:
Long by 5, wide by 5; Long by 10, wide by 10; Long by 15, wide by 10; Long by 15, wide by 15; Long by 20, wide by 20;
Long by 25, wide by 15; Long by 25, wide by 20; Long by 25, wide by 25; Long by 30, wide by 30; Long by 40, wide by 40;
Diameter 102mm; 3 inches of diameters; 4 inches of diameters; 5 inches of diameters; 6 inches of diameters; 7 inches of diameters;
8 inches of diameters; 9 inches of diameters; 12 inches of diameters; 15 inches of diameters; 18 inches of diameters; Or the like.
It is following to use seed crystal to induce freezing method to produce the embodiment of silicon single crystal of the present invention.
Bottom at the quartz crucible of vertical direction solidification equipment; Tiling and fixedly one deck comprise the inculating crystal layer of a plurality of monocrystalline silico briquettes; Wherein, the monocrystalline silico briquette has identical crystal orientation orientation, and closely arranges the inculating crystal layer that forms the about 25mm of thickness; Inculating crystal layer covers part crucible bottom at least, the for example crucible bottom of 1～100% area.Silicon material and doping agent are placed at the seed crystal top.In the time of the heat fused raw material, make the top of inculating crystal layer, the about partial melting of 10mm thickness for example, and that rest part keeps is solid-state.Cool off the crucible bottom at seed crystal place then, make to solidify to begin to take place and expand,, obtain the doped monocrystalline silicon of employing seed crystal revulsion of the present invention to solidifying completion to the top from the solid-liquid interface place of the solid-state top of inculating crystal layer.
Another embodiment consistent with implementation method of the present invention is; Use the tabular monocrystalline silico briquette of the monoblock close, be flat on crucible bottom, as inculating crystal layer with crucible cavity bottom size; Then by with the method for above-mentioned use single crystal ingot inculating crystal layer, make molten silicon solidify the acquisition doped monocrystalline silicon.
Another embodiment similar with implementation method of the present invention is; Use the tabular monocrystalline silico briquette of size, be flat on the crucible bottom center, as inculating crystal layer less than the monoblock of crucible bottom; Wherein, The area of tabular monocrystalline silico briquette can be about the about 10～95% of crucible bottom area, then by with the method for above-mentioned use single crystal ingot inculating crystal layer, make molten silicon solidify the acquisition doped monocrystalline silicon.At this moment, for guaranteeing not all fusings of seed crystal, the time of fusing and temperature need control carefully; So that utilize the thermal conductive resin of crystal silicon; With the high melting heat of molten silicon, keep infusible while of part seed crystal at least, bottom silicon raw material melting ratio identical or close horizontal plane is more abundant.Certainly, also can pay no attention to a small amount of unfused silicon material in bottom, and after solidifying, remove these unfused silicon material, obtain complete and continuous silicon single crystal entity through separation.
The another kind of embodiment of use seed crystal inductive of making silicon single crystal of the present invention is that the seed crystal that employing has to the bottom outside protrusion holds the crucible at position, as the molten silicon solidification crucible of vertical direction coagulation system, does seed crystal inductive direction and solidifies.Wherein, the seed crystal accommodation section occupies the extreme lower position in crucible, makes the single crystal seed of holding wherein in the heating field that lapse rate distributes, keep minimum temperature and keep its underpart solid-state; And the top fusing; Above solid-state seed crystal, form solid-liquid interface, cool off crucible bottom then, make to solidify and upwards take place and development along solid-liquid interface; Solidify fully up to molten silicon, obtain doped single crystal silicon ingot of the present invention.Adopt this mode, can reduce the consumption of seed crystal, and the control difficulty that reduces fusing and solidify.In this embodiment, the overall dimension that seed crystal holds its horizontal section, position is generally less than its height, still, also can select the overall dimension of its horizontal section to hold the position greater than its seed crystal highly.
A kind of improvement project to above-mentioned embodiment is; Above the seed crystal of crucible holds the position, the crucible intermediate location that horizontal sectional area vertically enlarges gradually is set, through this intermediate location; The crucible diapire holds the divide a word with a hyphen at the end of a line variation of position to tilt from seed crystal, is connected to the sidewall bottom.Then, place seed crystal to hold the position single crystal seed, make silicon material fusing and solidify, obtain doped single crystal silicon ingot of the present invention according to aforesaid method.
In silicon solidification crucible bottom the crystal selector position being set, making molten silicon begin to solidify from the crystal selector position, is another embodiment of the present invention.In this scheme; The crystal selector position forms the less cavity part of protruding on the crucible diapire in a horizontal section downwards; It processes the profile of crystal selector, for example, and spiral crystal selector or semispiral type crystal selector or tilting crystal selector or limitation of size type crystal selector or cucurbit serial type crystal selector shape; Its closed bottom, other parts that are connected to the crucible diapire suitable for reading.Because stray crystal can be reduced in the crystal selector position in the process of solidifying, strengthen the superiority in advantage crystal orientation, can obtain marshalling degree height, the specific high-quality silicon single crystal in crystal orientation.
When using the crucible at band crystal selector position; Its improved a kind of embodiment is above the crystal selector position; Also include the intermediate location that a horizontal section increases from top to bottom gradually, through this intermediate location, less crystal selector position, horizontal section is connected to the crucible wall bottom.The crucible of this mode, the sudden change turnover has been avoided occurring in the top, crystal selector position of diapire, and local temperature or the heat radiation cataclysm of having avoided the sudden change turnover to cause make crystal growth keep uniformity.
Through above-mentioned several kinds of modes, can obtain adulterated silicon single crystal ingot of the present invention (entity).Wherein, use the mode of seed crystal or the mode of crystal selector, the crystal mass of acquisition is better.
Seed crystal of the present invention holds the position, the crystal selector position has than the less size of crucible main body usually; The less horizontal section size and the height that comprise the cavity that it surrounds; For example, its horizontal section has the overall dimension of about 0.5～8cm, and the height of 1～20cm.Bigger size will consume more seed crystal or prolong the crystal growth cycle.
Adulterated silicon single crystal ingot of the present invention is applicable to makes high performance semiconductor wafer and device, and for example diode, thyristor, particularly photoelectricity are with wafer and sensitive cell.
As an embodiment, form at least one tabular crystal, i.e. wafer through the solid entity that cuts silicon ingot of the present invention; Choose wantonly and on wafer surface, implement cleaning step; Choose wantonly and on wafer surface, implement the decorative pattern step, promptly form the matte that reduces luminous reflectance in wafer surface; Optional to wafer enforcement heat treatment step, wherein, thermal treatment can further improve the performance of wafer; Form p-n junction, for example pass through surface doping; The optional ARC that deposits from the teeth outwards; Optional formation is selected from one deck at least of back surface field and passivation layer, for example through the aluminum sinter step; And on wafer, form conductive contact, wherein, conductive contact can be connected to each other to the conduction line or belt, thus, can produce sensitive cell by the wafer of producing according to the crystal silicon ingot of embodiment of the present invention.Passivation layer is the layer that has the interface with the naked wafer surface of the dangling bonds that maintains surface atom.The example of the passivation layer on the silicon comprises silicon nitride, silicon-dioxide and amorphous silicon.This layer is also thinner, perhaps transparent to only than 1 micron usually, perhaps as anti-reflecting layer.
In for example using photronic typical case of p type silicon wafers and general method, make wafer under high temperature, be exposed to suitable n type doping agent in a side, thereby in the front side of wafer or receive flash ranging to form emitter layer and p-n junction.For further improving photoabsorption, can apply optional ARC in the front side of wafer usually, for example silicon nitride provides surface and/or the passivation of body phase simultaneously sometimes.
Be exposed to the current potential that luminous energy produces in order to utilize through p-n junction, sensitive cell provides the preceding electrical contact of conduction usually at the front surface of wafer, and the back electrical contact of conduction is provided on the back surface of wafer.Electrical contact or title conductive contact are processed by the metal of conduction usually, and continuity connects into the conduction line or belt each other.
Those skilled in the art is obvious; Under the situation that does not depart from scope of the present invention or design; Can make various modifications and distortion to composition, the method for manufacture of the polysilicon that disclosed, and can be in order to process various semiconductor elements, devices such as including but not limited to diode, triode, thyristor, sensitive cell.Wherein, As an example; The thyristor element is on silicon single crystal of the present invention, to form at least 3 group p-n junctions and additional conductive contact (or line, band), and thyristor is with above-mentioned thyristor component package, draws electrical lead and connect and go up additional other semiconductor components and devices.
Claims (10)
1. adulterated direction solidified cast silicon single crystal, the doping agent that it contains optional at least a element in III family and V group element is characterized in that also being doped with concentration is 0.2～4*10
17Cm
3Carbon, 0.1～12*10
16Cm
3Nitrogen, 0.5～20*10
17Cm
3Oxygen, 0.2*10
16～1*10
20Cm
-3Germanium.
2. according to 1, it is characterized by, impurity concentration is by with next group at least a further preferred in impurity level: nitrogen 1.5～4.5*10
15Cm
-3, carbon 0.5～2*10
17Cm
-3, oxygen 1～10*10
17Cm
-3With germanium 1～50*10
16Cm
-3
3. according to 1, it is characterized by, also contain hydrogen.
4. the method for the silicon single crystal of production claim 1～3 includes step:
In including the direction solidified cast device of graphite heater, the quartz crucible fusing of using its inwall to scribble nitrogenous disengaging coating is added with the silicon raw material of an amount of germanium, the nitrogenous raw material of optional interpolation; The carbonaceous raw material of optional interpolation; Optional oxygen containing raw material, the optional atmosphere that nitrogenous element is provided, the optional atmosphere that carbon elements is provided of adding; The optional atmosphere that contains oxygen element that provides; The cooling raw material melted makes its side that makes progress from the initial position of solidifying of crucible bottom solidify as direction, obtains adulterated casting monocrystalline silicon of the present invention.
5. the method for the silicon single crystal of production claim 1～3 includes step:
Silicon single crystal monoblock or a plurality of monocrystalline silico briquette are laid on crucible bottom so that lack the mode of cover part crucible bottom, as seed crystal;
The silicon raw material of the described target impurity of part places on the seed crystal with being mixed with at least;
The silicon raw material in the thermal field that provides lapse rate to distribute, heat fused crucible and the top of seed crystal keep lower section solid-state constant of seed crystal simultaneously;
Cool off the melt in the described crucible, melt is upwards solidified as direction from the position that the solid-state and molten silicon of seed crystal has a common boundary, obtain adulterated casting monocrystalline silicon of the present invention.
6. the method for the silicon single crystal of production claim 1～3 includes step:
The seed crystal that provides diapire to include downward protrusion holds the crucible at position, places this seed crystal to hold the position single crystal seed, and the raw silicon of the described target impurity of part places on the single crystal seed with being mixed with at least;
The thermal field that provides lapse rate to distribute, the top of heat fused raw silicon and single crystal seed keeps the solid-state constant of single crystal seed lower section simultaneously; Cool off the melt in the described crucible, melt is upwards solidified as direction from the position that the solid-state and molten silicon of single crystal seed has a common boundary, obtain adulterated casting monocrystalline silicon of the present invention.
7. the method for the silicon single crystal of production claim 1～3 includes step:
The crucible at the crystal selector position that diapire includes downward protrusion is provided, and the raw silicon of the described target impurity of part places in the crucible that comprises crystal selector position cavity with being mixed with at least;
The thermal field that provides lapse rate to distribute, the heat fused raw silicon;
Cool off the melt in the described crucible, melt is solidified as direction from crucible bottom crystal selector position is bottom-up, obtain adulterated casting monocrystalline silicon of the present invention.
8. a semiconductor element includes but not limited to the brilliant unit of diode, the brilliant unit of thyristor, sensitive cell sheet, it is characterized in that the p-n junction that it includes the described silicon single crystal of claim 1～3 and is formed by this silicon single crystal.
9. a semiconducter device includes but not limited to diode, thyristor, sensitive cell, it is characterized in that including the described silicon single crystal of claim 1～3.
10. be used to make the purposes that includes but not limited to crystal or wafer, diode, thyristor, sensitive cell sheet or photronic semiconductor element, device that comprises p-n junction according to the silicon single crystal of claim 1～3.
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| CN104047052A (en) * | 2013-03-11 | 2014-09-17 | 三菱综合材料株式会社 | Silicon member for semiconductor apparatus and method of producing same |
| CN109306509A (en) * | 2018-11-27 | 2019-02-05 | 江苏拓正茂源新能源有限公司 | A kind of solar battery mono-crystal silicon materials preparation process |
| CN111910248A (en) * | 2020-07-14 | 2020-11-10 | 江苏协鑫硅材料科技发展有限公司 | Ingot casting single crystal seed crystal, cast single crystal silicon ingot and preparation method thereof, cast single crystal silicon slice and preparation method thereof |
| WO2021037275A1 (en) * | 2019-08-29 | 2021-03-04 | 浙江大学 | Monocrystalline silicon wafer containing germanium and nitrogen impurities, preparation method for monocrystalline silicon wafer, and integrated circuit comprising silicon wafer |
| CN113846378A (en) * | 2021-09-29 | 2021-12-28 | 西安奕斯伟材料科技有限公司 | Method for producing nitrogen-doped single crystal silicon |
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| CN104047052A (en) * | 2013-03-11 | 2014-09-17 | 三菱综合材料株式会社 | Silicon member for semiconductor apparatus and method of producing same |
| US9878915B2 (en) | 2013-03-11 | 2018-01-30 | Mitsubishi Materials Corporation | Silicon member for semiconductor apparatus and method of producing the same |
| CN104047052B (en) * | 2013-03-11 | 2018-10-19 | 三菱综合材料株式会社 | The manufacturing method of semiconductor device silicon parts and semiconductor device silicon parts |
| CN109306509A (en) * | 2018-11-27 | 2019-02-05 | 江苏拓正茂源新能源有限公司 | A kind of solar battery mono-crystal silicon materials preparation process |
| WO2021037275A1 (en) * | 2019-08-29 | 2021-03-04 | 浙江大学 | Monocrystalline silicon wafer containing germanium and nitrogen impurities, preparation method for monocrystalline silicon wafer, and integrated circuit comprising silicon wafer |
| CN111910248A (en) * | 2020-07-14 | 2020-11-10 | 江苏协鑫硅材料科技发展有限公司 | Ingot casting single crystal seed crystal, cast single crystal silicon ingot and preparation method thereof, cast single crystal silicon slice and preparation method thereof |
| CN111910248B (en) * | 2020-07-14 | 2022-02-18 | 江苏协鑫硅材料科技发展有限公司 | Ingot casting single crystal seed crystal, cast single crystal silicon ingot and preparation method thereof, cast single crystal silicon slice and preparation method thereof |
| CN113846378A (en) * | 2021-09-29 | 2021-12-28 | 西安奕斯伟材料科技有限公司 | Method for producing nitrogen-doped single crystal silicon |
| CN113862776A (en) * | 2021-09-30 | 2021-12-31 | 西安奕斯伟材料科技有限公司 | Equipment and method for manufacturing nitrogen-doped monocrystalline silicon |
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