CN104818524A - Method and heater for improving quality of monocrystal silicon grown by Czochralski method - Google Patents
Method and heater for improving quality of monocrystal silicon grown by Czochralski method Download PDFInfo
- Publication number
- CN104818524A CN104818524A CN201510210421.1A CN201510210421A CN104818524A CN 104818524 A CN104818524 A CN 104818524A CN 201510210421 A CN201510210421 A CN 201510210421A CN 104818524 A CN104818524 A CN 104818524A
- Authority
- CN
- China
- Prior art keywords
- crucible
- heater
- crystal
- czochralski
- heater strip
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a method and a heater for improving quality of monocrystal silicon grown by Czochralski method. The method includes putting raw silicon into a crucible of a crystal furnace; heating the crucible to melt the raw silicon in the crucible by the heater and keeping a melt in a molten state; soaking a rod-shaped seed crystal in a solution; injecting inert gas to the liquid level of the melt and controlling furnace pressure; rotating the crucible and lifting the rod-shaped seed crystal reversely rotating relative to the crucible to obtain a cylindrical monocrystal silicon crystal, and controlling heating quantity along the depth direction of the crucible during crystal pulling to enable the temperature gradient of the melt from the growth interface to the bottom of the crucible to decrease. The heater is used for implementing the method. The method and the heater have the advantages that heat convection is reduced effectively, microdefects and deleterious impurities in the monocrystal silicon are reduced, the monocrystal silicon with low defects, ultralow oxygen and high minority carrier lifetime is obtained, cost is low and easiness in implementation is achieved.
Description
Technical field
The present invention relates to vertical pulling method monocrystalline silicon growing technology, particularly a kind of method and well heater improving the siliceous amount of monocrystalline growth with czochralski.
Background technology
Vertical pulling method Crystal Growth Technique (Czochralski, CZ method) is that raw silicon is put into quartz crucible, heating and melting in single crystal growing furnace, then is immersed in liquation by bar-shaped crystal seed (seed crystal).At a suitable temperature, the Siliciumatom in liquation along the crystallization of Siliciumatom arrangement architecture formation rule on solid-liquid interface of crystal seed, can become single crystal.Rotation slight for crystal seed is upwards promoted, the single crystal that the Siliciumatom in liquation can be formed above continues crystallization, and continues the atomic arrangement structure of its rule.If whole crystalline environment is stablized, the formation crystallization that just can go round and begin again, finally forms the neat single crystal silicon of a columniform atomic arrangement, i.e. silicon single crystal ingot.
Vertical pulling method single crystal growing is widely used in single crystal silicon semiconductor and solar monocrystalline silicon, along with vertical pulling method single crystal growing is to the large charging future development of major diameter, in prior art, in vertical pulling method monocrystalline silicon production, well heater is used for being incubated in melt raw material silicon and crystal pulling process, in prior art, general employing high purity graphite material, also uses C-C composite at present.Common graphite heater structure as shown in Figure 1, well heater comprises the heating body 1 of tubular and the electrode foot 2 be fixed on heating body and sole for subsequent use 3, heating body 1 offers the upper fluting 11 and lower fluting 12 circumferentially alternately arranged, heating body is divided into the many heater strips of connecting successively 13 by upper fluting and lower fluting, well heater processes on cylindric or barrel-shaped graphite idiosome, by even fluting, form width, consistency of thickness and longitudinal graphite heating bar bending back and forth, because each graphite heating bar resistivity is identical, sectional area is identical, heater strip generates heat evenly up and down,
In crystal pulling process, the quartz crucible of charge is placed in above-mentioned heater body, crucible top is open system, not insulation or heat insulation effect poor, and amount of heat is taken away in the flowing of protection gas, and well heater side and bottom high insulating effect, therefore, in quartz crucible, the temperature of melt is more and more higher with the depth down of melt, thus forming larger thermograde, temperature curve is as shown in a in Fig. 2, and the temperature of melt constantly raises with the depth down of melt, thus the thermal convection that thermograde is caused aggravation, and then defect concentration in crystal is caused sharply to strengthen; The chance that bath attacks quartz crucible causes the impurity oxygen in crucible to enter crystal with convection current increase in addition also significantly increases.
V (r)/G (r) is an important parameter in crystal pulling process, V is pulling rate, G is the thermograde striding across solid-liquid growth interface, r is crystal radius, show that V, G change with r, the size of V/G ratio determines type and the density size of the lattice imperfection in the crystal grown, the silicon single crystal of vacancy-like defects is formed when V/G is very large, the silicon single crystal of clearance type defect is formed when V/G is very little, from clearance type silicon single crystal to room type silicon single crystal, V/G has threshold value-(V/G) of a centre
criticalwhen V/G is just in time near this threshold value, room and all very low from the defect concentration of gap silicon, monocrystalline almost Perfect, but want working control to be difficult to such condition, if will ensure whole growth interface to control to such condition, that is almost impossible, therefore, in the actual production of silicon single crystal, do not seek perfect monocrystalline, but the hazard rating of defect will be controlled.
On whole growth interface, because the speed of cooling of single-crystal surface is faster, so, G (r) has increase tendency with monocrystalline center to edge, V/G has to edge the trend that diminishes with center, therefore, monocrystalline central position more easily forms vacancy-like defects, edge more easily forms clearance type defect, if crystal pulling state modulator is bad, V/G is made to be near threshold value, at this moment the monocrystalline pulled out will form room, center type, the monocrystalline of marginal gap type defect, the monocrystalline of the intersection of room and clearance type defect easily forms OISF ring, it makes single crystal silicon semiconductor cause component failure because of this large-sized defect.
On the other hand; melted silicon at the inwall of the quartz crucible of high-temperature area to corrode; the SiO2 of inwall enters in molten silicon; enter the O in melt and be brought to bath surface with the convection current of melt; and with the form of SiO volatilization enter protection gas in taken away by vacuum pump; the oxygen of about 1% is only had to be transported near growth interface with the flowing of melt and then to enter in silicon single crystal; the thermograde of melt is larger; the melt of the oxygen enrichment of crucible bottom is more easily brought near growth interface, and the oxygen level in the silicon of preparation is higher.
Although the oxygen precipitation that oxygen appropriate in single crystal silicon semiconductor is formed in device fabrication process has intrinsic gettering effect, thus the performance of device can be improved, but a large amount of oxygen precipitation that too high oxygen level is formed and the secondary defect induced reach certain size, the performance of device will be had a strong impact on, under there is situation while high defect concentration and hyperoxia, more easily form the swirl defect that just can observe of naked eyes and OISF ring, cause scrapping of device, therefore need the oxygen level in reduction silicon single crystal.And in sun silicon single crystal, although the processing temperature of battery is not high, time is not long yet, the amount of oxygen precipitation is little, but the minority carrier life time impact of the initial stage of oxygen precipitation on material is huge, and the combination of highdensity defect and hyperoxia, causes declining to a great extent of minority carrier life time, produce evil mind low effect phenomenon, have a strong impact on quality product.
In prior art, crucible top is open system, not insulation or heat insulation effect poor, and amount of heat is taken away in the flowing of protection gas, and well heater side and bottom high insulating effect, therefore, in crucible, the temperature of melt is more and more higher with the depth down of melt, thus form larger thermograde in melt inside, therefore, pass through the inventive method, control to add heat along crucible depth direction, thus overcome the large problem of upper and lower temperature difference of the prior art, the long interface of melt-growth is reduced to the thermograde of crucible bottom, thus reduce the thermograde G (r) of growth interface.
As shown in Figure 2, temperature curve a is the temperature curve produced under prior art, the temperature of melt constantly raises with the depth down of melt, along the degree of depth of melt, thermograde is always comparatively large, and the thermograde G (r) of growth interface is comparatively large, can form the monocrystalline of room, center type, marginal gap type defect, the monocrystalline of the intersection of room and clearance type defect easily forms OISF ring, and it makes single crystal silicon semiconductor cause component failure because of this large-sized defect.
And according to the inventive method, melt temperature is controlled, present as temperature curve b and c obviously reduces in the thermograde near growth interface, thus the thermograde G (r) of the growth interface of correspondence obviously reduces, when V remains unchanged, V/G becomes large, makes V/G away from stagnation point-(V/G)
critical, thus prevent the monocrystalline of room, formation center type, marginal gap type defect, avoid the intersection of room and clearance type defect to form OISF ring, improve minority carrier life time.
Control to add heat to be adjusted by the type of heating of adjustment well heater, preferably, what control described well heater adds heat, makes the top of well heater add heat and is greater than bottom and adds heat.
Simultaneously, because the thermal value of bottom is lower, crucible bottom melt temperature is reduced, extreme case, crucible bottom temperature is minimum, and temperature curve is as the temperature curve c of Fig. 2, and the melt of bottom oxygen enrichment can not produce thermal convection and flow to growth interface, at this moment the silicon single-crystal oxygen level grown is extremely low, greatly reduces the oxygen level of silicon single crystal.
Make the top of well heater add heat to be greater than bottom and to add heat and can be realized by zone heating, that namely strengthens top adds heat, but in order to simplify transformation, reduces costs, optimum situation uses the integral type well heater identical with in prior art, but undergo technological transformation to heater strip wherein.
In order to realize the inventive method, present invention also offers a kind of well heater improving the siliceous amount of monocrystalline growth with czochralski, the heating body comprising tubular and the electrode foot be fixed on heating body, described heating body offers the upper fluting and lower fluting circumferentially alternately arranged, heating body is divided into many heater strips of connecting successively by described upper fluting and lower fluting, and the heat that described heater strip is positioned at the generation of described heating body upper part is greater than the heat being positioned at bottom and producing.
Open Side Down for described upper fluting, the opening upwards of lower fluting.
The heater strip of existing graphite heater generates heat evenly up and down, again because the insulation situation that body of heater is upper and lower is different, thus cause the melt upper and lower temperature difference in crucible large, during use, be difficult to G (r) be controlled in less scope, and when well heater of the present invention is applied in existing crystal furnace, due to how lower few on the heat energy that well heater itself produces, just in time not good corresponding with existing crystal furnace oral area Insulation, thus the melt upper and lower temperature difference in crucible is reduced, thermograde is declined, realize described in the inventive method, in crystal pulling process, control to add heat along crucible depth direction, the long interface of melt-growth is reduced to the thermograde of crucible bottom.
According to heating power W=I
2r, R=ρ * l/S, ρ is resistivity of material, l is resistance length, S is the sectional area of resistance, and after powered up, the heat mode that the heat that top is produced is greater than bottom generation mainly contains sectional area, length and these three kinds of modes of resistivity of changing heater strip to the heater strip of connecting for making these.
The change of sectional area can be realized by the thickness and width changing heater strip, wherein, electric current flows in the heater strip of series connection, comprises the heat that the transverse current between each heater strip longitudinal current and heater strip produces, preferably, the wall thickness of described heating body becomes large from top to bottom gradually.Thus make each heater strip upper-thin-lower-thick.For the ease of manufacturing, making the wall thickness of heating body become large mode from top to bottom gradually has, and keeps the internal diameter of heating body constant, makes this body diameter of heating up-small and down-big by outside grinding; Keep the external diameter of heating body constant, make the internal diameter of heating body up big and down small by interior digging; Keep the medullary ray of heating body wall thickness constant, adjust internal-and external diameter, make external diameter up-small and down-big, internal diameter is up big and down small simultaneously.
Preferably, the aperture of described upper fluting and lower fluting is widened from bottom to top gradually.Thus make the heater strip between fluting and lower fluting up-narrow and down-wide.
Preferably, the distance on the edge, top of the bottom land distance heating body of each upper fluting is less than the distance on the edge, the end of the bottom land distance heating body of each lower fluting.
Above-mentioned three kinds of modes can change the cross section that in heater strip, electric current passes through, the cross section of heating body upper part is made to be less than bottom, thus realize described heater strip be positioned at described heating body upper part produce heat be greater than be positioned at bottom produce heat, realization can be combined separately through one or more modes.
During well heater energising, galvanic current flows into from the electrode foot of positive pole by well heater, and along 2 directions, by the heater strip of series connection, well heater is flowed out from negative electrode pin, for reducing the heating of well heater bottom, preferably, arbitrary a pair adjacent heater strip forms a U-shaped heater strip, what wherein have upper fluting is upper U-shaped heater strip, what have lower fluting is lower U-shaped heater strip, count from the electrode foot of well heater, by starting lower U-shaped heater strip counting clockwise or counterclockwise, and what electrode foot interval was separated by is U-shaped heater strip under strange ordinal number, all the other are U-shaped heater strip under even ordinal number, under described even ordinal number, the end of U-shaped heater strip, is along the edge, the end higher than heater strip U-shaped under strange ordinal number.
Preferred further, the bottom level of the bottom level of U-shaped heater strip U-shaped heater strip under being not less than strange ordinal number under even ordinal number.
Can also realize generating heat up and down inequality by the material adjusting heater strip top and the bottom, preferably, described heater strip is spliced by upper and lower, and the resistivity on top is greater than the resistivity of bottom.Whole well heater is formed by Graphite Powder 99 compacting, and upper and lower uses the Graphite Powder 99 of different resistivity, or during extrusion forming, the density of upper and lower part is different, and top is loose, bottom is tight, and the resistivity on top namely can be made to be greater than the resistivity of bottom.
The thermograde of melt can also be reduced by the insulation situation of the top and the bottom of insulated tank outside adjustment well heater, preferably, the top insulation layer thickness being arranged on the insulated tank outside heater body is greater than bottom insulation layer thickness.The lagging material heat transfer coefficient that top thermal insulation layer adopts is less than the lagging material heat transfer coefficient that bottom thermal insulation layer adopts.Arrange insulation layer thickness to be controlled by the number of plies being wound around lagging material.Thus the heat insulation effect realizing the top of insulated tank comparatively better, reduces the thermograde of melt in bottom further.
Use well heater of the present invention, structure is similar to existing integral type well heater, can directly be applied in existing crystal furnace, technology maturation, and be easy to mate with existing crystal furnace, do not set up circuit or parts, improvement cost is low.
In order to improve monocrystalline quality further, need to control crystal pulling parameter:
Pressure in single crystal growing furnace is called furnace pressure, furnace pressure is by regulating the aperture adjustment of vacuum valve, and furnace pressure is less, and the volatilization of bath surface SiO is easier, oxygen level in the silicon single-crystal grown is lower, but furnace pressure is lower, the stability of liquid level is also lower, draws that to put number of times also more, single crystal growing difficulty increases, need to select in suitable scope, preferably, by controling of the pressure of the oven at 10 ~ 25Torr.
Rare gas element is adopted to do protection gas in crystal pulling process, generally select argon gas as protection gas, protection gas enters from furnace roof, main chamber is entered through neck, liquid level is flowed to through heat shielding, and the gap from heat shielding between edge and liquid level is flowed out, protection gas can maintain stable furnace pressure, constantly can take away again the SiO that liquid level volatilizes, inert gas flow more easily takes away SiO more greatly, but increase inert gas flow, the consumption of rare gas element increases, vacuum pump load increases, bring the increase of crystal pulling cost, therefore, also need to control in suitable scope, preferably, inert gas flow is controlled at 50 ~ 150slpm.
The forced convection that crucible rotation produces produces restraining effect to thermal convection, thus play stable melt, reduce the effect of crystal pulling difficulty, improve the rotating speed of crucible, draw and put number of times and obviously reduce, but the relative flowing between inner wall of quartz crucible with melt increases, and viscous layer is therebetween thinning, and more oxygen can enter in melt, thus cause the oxygen level in silicon single-crystal to increase, take into account to fall oxygen and falling crystal pulling difficulty, preferably, the rotating speed of crucible is 7 ~ 12rpm.
Seed crystal rotates in the other direction relative to crucible, make that crystal growth zone is relative with other region to be isolated, reduce the fluctuation of melt convection to the impact of monocrystalline stable growth, the rotating speed increase of seed crystal is conducive to crystal pulling, also can play the effect of stirring simultaneously, the Impurity Distribution be conducive in melt is even, improve the homogeneity of the radial resistivity of monocrystalline, but limit by the transient equilibrium of single crystal growing furnace lifting head, the excessive crystalline substance change of team causes rocking and swinging of monocrystalline, such as semiconductor monocrystal stove crystalline substance turns and can reach 30rpm, solar energy single crystal stove generally can only reach 15rpm, preferably, the rotating speed of seed crystal is 10 ~ 30rpm.
Bushing position determines the position of the growth liquid level of crystal, crucible position is lower, mean that crucible moves to heater base, be conducive to the reduction of thermograde in melt, when crucible bottom is in cold zone, defect in silicon and oxygen level greatly reduce, but crucible potential drop is low, growth liquid level moves toward high-temperature zone, the crucible internal walls of liquid level has higher temperature, and monocrystalline crystallizing field is the zero pour of silicon, temperature-resistant, such liquid level radial direction thermograde increases, surface convection current increases, fluctuation increases, draw and put number of times showed increased, for taking into account into the quality of brilliant and monocrystalline, preferably, the position of the crucible relative heater of adjustment single crystal growing furnace, growth liquid level is made to be 50 ~ 150mm from the vertical range on edge, well heater top.
Beneficial effect of the present invention:
The method improving the siliceous amount of monocrystalline growth with czochralski of the present invention, by controlling to add heat along crucible depth direction, the long interface of melt-growth is reduced to the thermograde of crucible bottom, thus reduce the thermograde in the melt of growth interface, and then reduce the thermograde G (r) of growth interface, make V/G become large, V/G is away from stagnation point-(V/G)
criticalthus prevent the monocrystalline of room, formation center type, marginal gap type defect, avoid the intersection of room and clearance type defect to form OISF ring, reduce thermal convection simultaneously, reduce the microdefect in silicon single crystal and detrimental impurity, prepare the silicon single crystal of low defect, Ultra Low-oxygen, high minority carrier life time; Namely the well heater of the application of the invention can realize the inventive method, and is easy to mate with existing crystal furnace, and do not set up circuit or parts, improvement cost is low.
Summary of the invention
The invention provides a kind of method improving the siliceous amount of monocrystalline growth with czochralski, by improving the thermal field design of single crystal growing furnace and optimization to crystal pulling technique, realizing the manufacture of silicon single crystal of low defect, Ultra Low-oxygen, high minority carrier life time.
Improve a method for the siliceous amount of monocrystalline growth with czochralski, comprise step: raw silicon is dropped in the crucible of crystal furnace; Heater heats crucible melts the raw silicon in crucible and keeps melt in molten state; Bar-shaped seed crystal is immersed in liquation; Pass into rare gas element to melt liquid level, control furnace pressure; While rotate crucible, promote the bar-shaped seed crystal of relative crucible reverse rotation, obtain columniform single crystal silicon; Control to add heat along crucible depth direction, the long interface of melt-growth is reduced to the thermograde of crucible bottom.
Accompanying drawing explanation
Fig. 1 is the structural representation of the well heater of prior art.
Fig. 2 is the thetagram of the difference change that different heating mode is brought.
Fig. 3 is the local structure schematic diagram of the well heater of embodiment 1.
Fig. 4 is the cross-sectional structure schematic diagram of the well heater of embodiment 2.
Fig. 5 is the local structure schematic diagram of the well heater of embodiment 2.
Fig. 6 is the local structure schematic diagram of the well heater of embodiment 3.
Fig. 7 is the PL detection figure of the silicon single crystal using the well heater of embodiment 3 to produce.
Fig. 8 is the PL detection figure of the silicon single crystal using the well heater of prior art to produce.
Embodiment
Embodiment 1
The well heater of the present embodiment is applied on 20 cun of quartz crucibles, 20 cun of quartz crucible height 380mm, charging capacity 135KG, draws N-type, <100> crystal orientation, resistivity 0.8 ~ 4.5 Ω cm, the silicon single-crystal that diameter is 6.5 inches.
As shown in Figure 3, the width top of the heater strip 13 of the present embodiment is 1/3rd of bottom, broadband, middle part is 2 times of top, broadband, bottom is 3 times of top, heating body 1 internal-and external diameter is unanimous between the higher and lower levels, heater strip 13 thickness is constant, the height of heating body 1 is 380mm, the degree of depth of the fluting of upper fluting 11 and lower fluting 12 meeting at the bottom of H=L at the bottom of=3L top=3H pushes up, the distance on the edge, top of the bottom land distance heating body of upper fluting is H top, the distance on the edge, the end of the bottom land distance heating body of lower fluting is at the bottom of H, said structure makes the thermal value on the top of heater body 1 be greater than the thermal value of bottom, in conjunction with the situation of top rapid heat dissipation, thus make the melt upper and lower temperature difference in crucible little, thermograde is remained on very little.
The method of the siliceous amount of improvement monocrystalline growth with czochralski of the present embodiment, step comprises, and is dropped into by raw silicon in the crucible of crystal furnace, adjusts initial crucible position, to guarantee that first the material of crucible bottom melts, thus avoids Lou expecting; Heater heats crucible melts the raw silicon in crucible and keeps melt in molten state; Bar-shaped seed crystal is immersed in liquation; Pass into rare gas element as shielding gas to melt liquid level, argon flow amount is 90slpm, and furnace pressure is 13Torr; While rotate crucible, promote the bar-shaped seed crystal of relative crucible reverse rotation, the rotating speed of seed crystal is 10rpm, and the rotating speed of crucible is 8rpm, obtains columniform single crystal silicon.
Crystal pulling result is draw for 2 times to put, yield rate 87.5%, get head, in, tail sample detection, oxygen level is respectively, and 14.5,10.5,12.1ppma, minority carrier life time is respectively 11500, and 9500,4780us, PL detects and does not find donut or concentric(al) circles, and high-temperature thermal oxidation is tested, and does not find swirl defect and OISF ring, in battery processing, whole monocrystalline does not find poor efficiency sheet.
Embodiment 2
The well heater of the present embodiment is applied on 18 cun of quartz crucibles, the height 350mm of 18 cun of quartz crucibles, charging capacity 90KG, draws N-type, <111> crystal orientation, repeatedly crystal pulling, front 36 inches, target resistivity 45 ~ 30 Ω cm, finally draws 5 inches, pull remaining material, target resistivity 45 ~ 15 Ω cm.
While the heater strip 13 bottom thickening of the present embodiment, bottom is widened, as shown in Figure 4, the wall thickness of heater body 1 becomes large from top to bottom gradually, top thickness is 3/4 of bottom thickness, as shown in Figure 5, by adjusting upper fluting and lower fluting, heater strip 13 width top is made to be 3/4 of bottom, the whole sectional area at heater body 1 top and the section area ratio of bottom are 9:16, heater height 350mm, and the degree of depth of the fluting of upper fluting 11 and lower fluting 12 is to meet at the bottom of H=4H top, said structure makes the thermal value on the top of heater body 1 be greater than the thermal value of bottom, in conjunction with the situation of top rapid heat dissipation, thus make the melt upper and lower temperature difference in crucible little, thermograde is remained on very little.
The method of the siliceous amount of improvement monocrystalline growth with czochralski of the present embodiment, except using the well heater of the present embodiment, also increasing bottom heater to guarantee not leak material, material power opens 25KW, the well heater material peak power 75KW of the present embodiment, material terminates, close bottom heater, except crystal pulling parameter adjustment, crystal pulling process is identical with embodiment 1, crystal pulling technique condition is, furnace pressure is 15Torr, and argon flow amount is 100slpm, and the rotating speed of seed crystal is 25rpm, the rotating speed of crucible is 8rpm, grows liquid level position on well heater along 90mm.
Get 4 sample detection, 4 head of single crystal oxygen levels are respectively: 13.5,13.7,13.3,13.1ppma, and afterbody oxygen level is respectively: 11.5,10.8,11.1,12.7ppma, and high-temperature thermal oxidation is tested, and does not find thermooxidizing swirl defect and OISF ring.
Embodiment 3
The well heater of the present embodiment is applied in 22 cun of quartz crucibles, 22 cun of quartz crucible height 420mm, charging capacity 200KG, draws P type, <100> crystal orientation, resistivity 1 ~ 3 Ω cm, the solar energy silicon single crystal that diameter is 8 inches.
As shown in Figure 1, the arbitrary a pair adjacent heater strip of well heater forms a U-shaped heater strip, what wherein have upper fluting is upper U-shaped heater strip 4, what have lower fluting is lower U-shaped heater strip 5, count from the electrode foot of well heater, by starting clockwise or counterclockwise lower U-shaped heater strip counting, and electrode foot 2 interval is separated by is U-shaped heater strip 51 under strange ordinal number, and all the other are U-shaped heater strip 52 under even ordinal number.
The well heater of the present embodiment, as shown in Figure 6, L idol=280mm in figure, L is strange=420mm, H idol=2H very=2L, L are heater strip broadband, said structure makes the thermal value on the top of heater body 1 be greater than the thermal value of bottom, in conjunction with the situation of top rapid heat dissipation, thus make the melt upper and lower temperature difference in crucible little, thermograde is remained on very little.
The method of the siliceous amount of improvement monocrystalline growth with czochralski of the present embodiment, except using the well heater of the present embodiment, also increasing bottom heater to guarantee not leak material, material power opens 25KW, the well heater material peak power 80KW of the present embodiment, material terminates namely to close bottom heater, except crystal pulling parameter adjustment, crystal pulling process is identical with embodiment 1, furnace pressure is 13Torr, and argon flow amount is 90slpm, and the rotating speed of seed crystal is 10rpm, the rotating speed of crucible is 7rpm, isodiametric growth liquid level position on well heater along 90mm.
Crystal pulling result puts 1 time for drawing, crystal forming rate 89.5%, get head, in, tail sample detection, oxygen level is respectively 13.1,8.5,10.7ppma, body life time detects and is respectively 690,390,86us, PL detects and does not find donut or concentric(al) circles, and PL detects figure as shown in Figure 7, and high-temperature thermal oxidation is tested, do not find swirl defect and OISF ring, after being processed into battery, its battery conversion efficiency is 19.786%, and whole monocrystalline does not find evil mind poor efficiency sheet.
By the well heater of prior art, the well heater as Fig. 1 is applied in 22 cun of quartz crucibles, quartz crucible height 420mm, charging capacity 200KG, draws P type, <100> crystal orientation, resistivity 1 ~ 3 Ω cm, the solar energy silicon single crystal that diameter is 8 inches.
As shown in Figure 1, the arbitrary a pair adjacent heater strip of well heater forms a U-shaped heater strip, what wherein have upper fluting is upper U-shaped heater strip 4, what have lower fluting is lower U-shaped heater strip 5, count from the electrode foot of well heater, by starting clockwise or counterclockwise lower U-shaped heater strip counting, and electrode foot 2 interval is separated by is U-shaped heater strip 51 under strange ordinal number, and all the other are U-shaped heater strip 52 under even ordinal number.
The well heater of comparative example, in figure L idol=L strange=420mm, H idol=H is strange=L, L are heater strip broadband, said structure makes the thermal value of the top and the bottom of heater body 1 evenly, and the melt temperature gradient in crucible is larger, as shown in the temperature curve a in Fig. 2.
In comparative example, crystal pulling parameter is identical with embodiment 3, and furnace pressure is 13Torr, and argon flow amount is 90slpm, and the rotating speed of seed crystal is 10rpm, and the rotating speed of crucible is 7rpm, isodiametric growth liquid level position on well heater along 90mm.
Crystal pulling result puts 2 times for drawing, crystal forming rate 85.6%, get head, in, tail sample detection, oxygen level is respectively 19.8,13.5,15.7ppma, body life time detects and is respectively 590,190,36us, get head sample, after being processed into battery, its battery conversion efficiency is that 17.956%, PL detects figure as shown in Figure 8, find donut in the silicon single crystal clearly using the well heater of prior art to produce, head has evil mind poor efficiency sheet.
In sum, use the well heater of the present embodiment to complete the inventive method, realize the manufacture of silicon single crystal of low defect, Ultra Low-oxygen, high minority carrier life time, easily to realize and cost is lower.
Claims (10)
1. improve a method for the siliceous amount of monocrystalline growth with czochralski, comprise step: raw silicon is dropped in the crucible of crystal furnace; Heater heats crucible melts the raw silicon in crucible and keeps melt in molten state; Bar-shaped seed crystal is immersed in liquation; Pass into rare gas element to melt liquid level, control furnace pressure; While rotate crucible, promote the bar-shaped seed crystal of relative crucible reverse rotation, obtain columniform single crystal silicon; It is characterized in that, in crystal pulling process, control to add heat along crucible depth direction, the long interface of melt-growth is reduced to the thermograde of crucible bottom.
2. improve the method for the siliceous amount of monocrystalline growth with czochralski as claimed in claim 1, it is characterized in that, what control described well heater adds heat, makes the top of well heater add heat and is greater than bottom and adds heat.
3. improve the method for the siliceous amount of monocrystalline growth with czochralski as claimed in claim 1 or 2, it is characterized in that, by controling of the pressure of the oven at 10 ~ 25Torr, inert gas flow is controlled at 50 ~ 150slpm; The rotating speed of crucible is 7 ~ 12rpm, and the rotating speed of seed crystal is 10 ~ 30rpm.
4. improve the method for the siliceous amount of monocrystalline growth with czochralski as claimed in claim 1 or 2, it is characterized in that, the position of the crucible relative heater of adjustment single crystal growing furnace, makes growth liquid level be 50 ~ 150mm from the vertical range on edge, well heater top.
5. one kind is improved the well heater of the siliceous amount of monocrystalline growth with czochralski, the heating body comprising tubular and the electrode foot be fixed on heating body, described heating body offers the upper fluting and lower fluting circumferentially alternately arranged, heating body is divided into many heater strips of connecting successively by described upper fluting and lower fluting, it is characterized in that, the heat that described heater strip is positioned at the generation of described heating body upper part is greater than the heat being positioned at bottom and producing.
6. improve the well heater of the siliceous amount of monocrystalline growth with czochralski as claimed in claim 5, it is characterized in that, the aperture of described upper fluting and lower fluting is widened from bottom to top gradually.
7. the well heater of the siliceous amount of improvement monocrystalline growth with czochralski as described in claim 5 or 6, is characterized in that, the wall thickness of described heating body becomes large from top to bottom gradually.
8. the well heater of the siliceous amount of improvement monocrystalline growth with czochralski as described in claim 5 or 6, is characterized in that, the distance on the edge, top of the bottom land distance heating body of each upper fluting is less than the distance on the edge, the end of the bottom land distance heating body of each lower fluting.
9. the well heater of the siliceous amount of improvement monocrystalline growth with czochralski as described in claim 5 or 6, it is characterized in that, arbitrary a pair adjacent heater strip forms a U-shaped heater strip, what wherein have upper fluting is upper U-shaped heater strip, what have lower fluting is lower U-shaped heater strip, count from the electrode foot of well heater, by starting lower U-shaped heater strip counting clockwise or counterclockwise, and what electrode foot interval was separated by is U-shaped heater strip under strange ordinal number, all the other are U-shaped heater strip under even ordinal number, and under described even ordinal number, the end of U-shaped heater strip is along the edge, the end higher than heater strip U-shaped under strange ordinal number.
10. improve the well heater of the siliceous amount of monocrystalline growth with czochralski as claimed in claim 9, it is characterized in that, the bottom level of the bottom level of U-shaped heater strip U-shaped heater strip under being not less than strange ordinal number under even ordinal number.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510210421.1A CN104818524A (en) | 2015-04-28 | 2015-04-28 | Method and heater for improving quality of monocrystal silicon grown by Czochralski method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510210421.1A CN104818524A (en) | 2015-04-28 | 2015-04-28 | Method and heater for improving quality of monocrystal silicon grown by Czochralski method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104818524A true CN104818524A (en) | 2015-08-05 |
Family
ID=53728998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510210421.1A Pending CN104818524A (en) | 2015-04-28 | 2015-04-28 | Method and heater for improving quality of monocrystal silicon grown by Czochralski method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104818524A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106222736A (en) * | 2016-10-17 | 2016-12-14 | 宁夏协鑫晶体科技发展有限公司 | Heater for pulling of crystals |
| CN106637388A (en) * | 2015-11-03 | 2017-05-10 | 有研光电新材料有限责任公司 | Heat field structure for growth of low-dislocation single crystals by czochralski method and growing process of single crystal |
| CN106868584A (en) * | 2015-12-10 | 2017-06-20 | 有研半导体材料有限公司 | A kind of monocrystalline furnace resistor heater and the method that silicon single crystal is prepared using the resistance heater |
| CN107604430A (en) * | 2016-07-11 | 2018-01-19 | 上海超硅半导体有限公司 | Low oxygen content monocrystalline silicon growing method |
| CN107779945A (en) * | 2016-08-25 | 2018-03-09 | 上海新昇半导体科技有限公司 | Heater and single crystal pulling stove thermal field structure |
| CN112391676A (en) * | 2019-08-13 | 2021-02-23 | 新特能源股份有限公司 | Single crystal furnace thermal field, control method thereof and single crystal furnace |
| CN113061983A (en) * | 2021-04-21 | 2021-07-02 | 姜益群 | Crystal pulling furnace for semiconductor monocrystalline silicon |
| CN114592238A (en) * | 2020-12-02 | 2022-06-07 | 中国科学院上海微系统与信息技术研究所 | Single crystal growth equipment with moving heat preservation function and single crystal growth method |
| CN114592235A (en) * | 2022-03-04 | 2022-06-07 | 徐州康信软件技术有限公司 | Single crystal furnace for integrated circuit production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57106598A (en) * | 1980-12-18 | 1982-07-02 | Toshiba Corp | Semiconductor crystal growing device |
| CN85101043A (en) * | 1984-08-06 | 1987-01-10 | 索尼公司 | Single-crystal growing apparatus (equipment) |
| CN1304460A (en) * | 1998-06-05 | 2001-07-18 | Memc电子材料有限公司 | Electrical resistance heater for crystal growing apparatus |
| CN1317058A (en) * | 1998-06-26 | 2001-10-10 | Memc电子材料有限公司 | Electrical resistance heater for crystal growing apparatus and its method of use |
-
2015
- 2015-04-28 CN CN201510210421.1A patent/CN104818524A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57106598A (en) * | 1980-12-18 | 1982-07-02 | Toshiba Corp | Semiconductor crystal growing device |
| CN85101043A (en) * | 1984-08-06 | 1987-01-10 | 索尼公司 | Single-crystal growing apparatus (equipment) |
| CN1304460A (en) * | 1998-06-05 | 2001-07-18 | Memc电子材料有限公司 | Electrical resistance heater for crystal growing apparatus |
| CN1317058A (en) * | 1998-06-26 | 2001-10-10 | Memc电子材料有限公司 | Electrical resistance heater for crystal growing apparatus and its method of use |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106637388A (en) * | 2015-11-03 | 2017-05-10 | 有研光电新材料有限责任公司 | Heat field structure for growth of low-dislocation single crystals by czochralski method and growing process of single crystal |
| CN106868584A (en) * | 2015-12-10 | 2017-06-20 | 有研半导体材料有限公司 | A kind of monocrystalline furnace resistor heater and the method that silicon single crystal is prepared using the resistance heater |
| CN106868584B (en) * | 2015-12-10 | 2019-06-18 | 有研半导体材料有限公司 | A kind of monocrystalline furnace resistor heater and the method for preparing silicon single crystal using the resistance heater |
| CN107604430A (en) * | 2016-07-11 | 2018-01-19 | 上海超硅半导体有限公司 | Low oxygen content monocrystalline silicon growing method |
| CN107779945A (en) * | 2016-08-25 | 2018-03-09 | 上海新昇半导体科技有限公司 | Heater and single crystal pulling stove thermal field structure |
| CN107779945B (en) * | 2016-08-25 | 2020-11-27 | 上海新昇半导体科技有限公司 | Special-shaped heater and thermal field structure of single crystal pulling furnace |
| CN106222736A (en) * | 2016-10-17 | 2016-12-14 | 宁夏协鑫晶体科技发展有限公司 | Heater for pulling of crystals |
| CN112391676A (en) * | 2019-08-13 | 2021-02-23 | 新特能源股份有限公司 | Single crystal furnace thermal field, control method thereof and single crystal furnace |
| CN114592238A (en) * | 2020-12-02 | 2022-06-07 | 中国科学院上海微系统与信息技术研究所 | Single crystal growth equipment with moving heat preservation function and single crystal growth method |
| CN113061983A (en) * | 2021-04-21 | 2021-07-02 | 姜益群 | Crystal pulling furnace for semiconductor monocrystalline silicon |
| CN114592235A (en) * | 2022-03-04 | 2022-06-07 | 徐州康信软件技术有限公司 | Single crystal furnace for integrated circuit production |
| CN114592235B (en) * | 2022-03-04 | 2022-12-09 | 徐州康信软件技术有限公司 | Single crystal furnace for integrated circuit production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104818524A (en) | Method and heater for improving quality of monocrystal silicon grown by Czochralski method | |
| KR101997565B1 (en) | Method for producing monocrystalline silicon | |
| CN1904147B (en) | Method and apparatus for growing high quality silicon single crystal, silicon single crystal and silicon wafer | |
| CN103911654B (en) | The method preparing the monocrystal silicon of a diameter of more than 400mm | |
| JP6881571B2 (en) | Method for manufacturing n-type silicon single crystal | |
| WO2016078321A1 (en) | Method for preparing large size yb-yag laser crystal through kyropoulos method | |
| CN107460539A (en) | A kind of monocrystalline silicon production method of heater and the application heater | |
| CN107794563A (en) | A kind of vertical pulling method prepares the processing technology of monocrystalline silicon | |
| CN103422161A (en) | Preparation method of N-type solar silicon monocrystal material | |
| CN103173850A (en) | Monocrystalline silicon producing process | |
| CN106868584B (en) | A kind of monocrystalline furnace resistor heater and the method for preparing silicon single crystal using the resistance heater | |
| CN107109692A (en) | The manufacture method and solar cell of study on floating zone silicon used for solar batteries | |
| CN105951173A (en) | N type monocrystalline silicon crystal ingot and manufacturing method thereof | |
| CN204608210U (en) | A kind of well heater improving monocrystalline growth with czochralski silicon quality | |
| CN106498494A (en) | A kind of thermal field of MEMS making silicon single crystal material and preparation method | |
| WO2019003968A1 (en) | Method for producing silicon single crystal | |
| CN104746134B (en) | Using the n-type pulling single crystal silicon method of compensation silicon material | |
| CN109972200A (en) | Continuous pulling silicon single crystal growing method | |
| CN101812726A (en) | Method for preparing gallium-doped p-type crystalline silicon | |
| CN102560627A (en) | N-type czochralski silicon with uniform doping resistivity and preparation method thereof | |
| TWI827224B (en) | Nitrogen dopant feeding device, method and manufacturing system for nitrogen doped single crystal silicon rod | |
| CN101812728A (en) | Preparation method of n-type crystalline silicon | |
| CN102758253A (en) | Czochralski polycrystalline silicon or monocrystal silicon preparation technology | |
| CN102817071A (en) | Preparation technology of heat radiation resistant Czochralski polysilicon or monocrystalline silicon | |
| CN114164489B (en) | Method for manufacturing silicon single crystal rod |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160614 Address after: 710100 Changan District, Shaanxi Province, aerospace Road, No. 388, No. Applicant after: Le Ye PV energy Ltd Address before: 310013 room 72, 402 village, Qiushi village, Hangzhou, Xihu District, Zhejiang Applicant before: Tang Hao |
|
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150805 |
|
| RJ01 | Rejection of invention patent application after publication |