CN1016973B - Method and apparatus for manufacturing silicon single crystals - Google Patents
Method and apparatus for manufacturing silicon single crystalsInfo
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- CN1016973B CN1016973B CN 89102980 CN89102980A CN1016973B CN 1016973 B CN1016973 B CN 1016973B CN 89102980 CN89102980 CN 89102980 CN 89102980 A CN89102980 A CN 89102980A CN 1016973 B CN1016973 B CN 1016973B
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Abstract
The present invention relates to a method and apparatus for manufacturing silicon single crystals by the Czochralski method, including the steps of dividing a crucible containing molten silicon into an inner single crystal growing section and an outer material feeding section to allow said molten silicon to move slowly, and pulling a silicon single crystal from said single crystal growing section while continuously feeding silicon starting material to said material feeding section, the improvement wherein temperatures of said material feeding section and said molten silicon are maintained higher than a melting point of silicon by at least more than 12 DEG C.
Description
The invention relates to method and apparatus with Czochralski method (Czochralski method) preparation silicon single-crystal.
The method for preparing silicon single-crystal with Czochralski method is used so far, and it has become quite perfect technology.
According to this technology, as everyone knows, the silicon raw material of fusing added to quartz crucible after, seed crystal is contacted with the surface of melting charge, and the slow rand of seed crystal rotation limit is pulled out from melt, surface in contact is solidified, thereby and crystal is grown up obtain cylindrical monocrystalline.
Is P type or n N-type semiconductorN according to the purposes difference for the silicon single-crystal that makes production, and can add an amount of doping agent this moment in melting charge, for example boron, antimony or phosphorus.Yet this method that adds doping agent in silicon single-crystal is uneven, so that the position of silicon single-crystal is low more, and the concentration of doping agent is just high more.
Add the doping agent to silicon single-crystal wittingly except that above-mentioned, also introduce some impurity inevitably in preparation process, as oxygen and carbon, its amount is quite big.In other words, can improve semi-conductive characteristic and productive rate owing to introduce oxygen to silicon single-crystal, thereby hope is even to the content of bottom oxygen from the top in silicon single-crystal, the still common crystalline position concentration of hypoxemia more becomes low more.
This is owing to the melting charge of pulling out in the crucible along with silicon single-crystal is reducing, and the concentration of doping agent is reducing in the concentration of increase and oxygen in the crucible melting charge.As a result, doping agent increases gradually with oxygen and reduces gradually in the silicon single-crystal of pulling out and growing, thereby causes the performance of the silicon single-crystal produced to change along dip direction.
When for the composition specification requirement when strict, because the skewness of this doping agent and oxygen might make the yield rate of qualified wafer be reduced to below 50%.
As a kind of effective ways that overcome these shortcomings, known can be continuously or add the silicon raw material discontinuously so that the melting charge liquid level remains unchanged.For example, invention disclosed is exactly that a this continuously or intermittently adds the method that the silicon raw material simultaneously draws silicon single-crystal in day disclosure special permission 56-84397 number and 56-164097 number.
The former invention is about prepare the method for monocrystalline, is to immerse the raw material ingot in the fused raw material in crucible, and this raw material ingot is the monocrystalline of pulling out from the melting charge identical with the fused raw material composition, and have with constant speed under the identical form of desirable monocrystalline of growing.
On the other hand, latter's invention is the drawing device about monocrystalline, it is equipped with the melting charge feeder, a powdered sample feed-pipe is inserted in the instlated tubular outside thus, powdered sample is in the front end short stay and the fusing of powdered sample feed-pipe, discontinuously melting charge is supplied with crucible thus, but this method is not put to actual use owing to run into technical difficulty.
Preparing high-quality granular polycrystalline silicon has in recent years become possibility, and thinks that infeeding this grain silicon to fused raw material continuously with constant rate of speed is to be relatively easy to, and can consult day disclosure special permission 58-172289 number.Yet, cause from grain silicon and begin to solidify this fact that infeeding grain silicon continuously and generate monocrystalline with this method is impossible in principle because grain silicon drops on the fused raw material surface.The reason that is begun to solidify by the grain silicon that falls into is listed below:
(a) melt temperature is just above the fusing point of silicon during monocrystal pulling, and this point can be found out by the principle of pointing out previously.
(b) proportion of silicon is solid-state littler than liquid, so grain silicon swims in the melting charge surface.
(c) heat emissivity coefficient of silicon is solid-state bigger than liquid.
In other words, grain silicon swims in the molten silicon surface of temperature just above its zero pour, and heat is shed rapidly by grain silicon with the radiant heat form like this, thereby solidification is around the development of buoyant grain silicon.In addition, the wave that is caused by falling into of grain silicon also causes the generation problem.
On the other hand, the oxide semiconductor field of day disclosure special permission 56-88896 number and 58-36997 invention disclosed is known.According to these inventions, it is little to draw the crystalline diameter, can use the little metallic crucible of a kind of dimorphism like this, and this dimorphism crucible can directly adopt induction heating, has avoided melt to solidify in the middle of crucible thus.Yet the diameter owing to pulling monocrystal under the situation of silicon single-crystal is big, cost is high and reason such as contaminations occurs can not use metallic crucible, so generally uses highly purified quartz crucible.So this induction heating can not be used to prepare silicon single-crystal.
On the other hand, as if a day disclosure special permission 58-130195 invention disclosed adopts binode configuration quartz crucible, can exempt the solidification in the raw material melt portions at first sight.Yet pointed as day disclosure special permission 62-241889 number (page 2,12-16 capable " problem that the present invention solved "), the freezing problem with the melting charge surface contact portion in interior crucible does not still solve.
In addition, according to this invention, the silicon material feeding tube be inserted in interior and outer crucible between, the supply of raw material is to carry out in the outside of interior crucible by this feed-pipe that is immersed in the melting charge like this.Use this method of feeding, although be heated to high temperature, the silicon raw material can transient melting on the melting charge surface yet, and this solid feed gathers together in feed-pipe like this.In case this gathering taken place, will cause agglomeration problems between the particle and between raw material and feed-pipe inwall, continuous feeding can not be carried out.Owing to these reasons, this invention does not also try out so far.
63-95195 number disclosed invention of day disclosure special permission is the improvement to foregoing invention (day disclosure special permission 58-130195 number).This invention is to constitute like this, makes crucible inside be separated into crystal growth district and raw material melting area with toroidal membrane, and one adds particulate material towards the raw material melting area and simultaneously carries out crystal growth.Improvement to 58-130195 number invention of day disclosure special permission is, second ring heater is placed in crucible bottom solidifies and be convenient to its fusing with the raw material that prevents to add.Yet, invent freezing problem even the not thoroughly solution so far that begins from contact part in the dividing plate inboard with the melting charge surface according to this.
With foregoing invention (day disclosure special permission 58-130195 number and 63-95195 number) similar also comprise (Ann.ReV.Mater.Sci.) invention introduced of the paper of 1987 the 17th volume 273-279 pages or leaves of day disclosure utility model 59-141578 number and day disclosure 62-241889 number disclosed invention of special permission and " material supply section academic year comments ".First invention (day disclosure utility model 59-141578 number) provides, and annulation is floating in melting charge or melt.Yet, in this invention, between monocrystal pulling district and particulate material intake zone, melt convection is arranged below float ring, and the temperature in the float ring outside just reaching the fusing point that is higher than silicon in principle, it equates substantially with the temperature in monocrystal pulling district.Like this, do not solve fully by this basic problem of solidifying that begins in bath surface buoyant grain silicon.In addition, the development problem of solidifying that is begun by float ring does not solve yet, as specification sheets (day disclosure special permission communique 62-241889 number, " problem of the present invention's solution " second invention, 12-16 is capable) in point out like that, and only solved the wave problem.
On the other hand, second invention (day disclosure special permission 62-241889 number) provided along the vertical channel device in the crucible outside so that the through hole by crucible infeeds the silicon raw material to crucible.Yet the volume of the raw material melting area of this vertical channel is too little, if so that silicon raw material continuously feeding with very high latent heat of fusion, finally melt raw material again.In addition, the melting charge surface is approached in the hole, and the melt of different concns by convective zone and directly is transported to solid-liquid interface like this, so is easy to cause change in concentration, thereby hinders the growth of high quality crystal.In addition, this invention needs the processing quartz crucible, and process cost are very high, has therefore increased expense.
Two crucibles and fixed and float type stripper loop are adopted in the invention of being commented in paper (" material supply section academic year comments ", 1987, volume 17, the 273-279 pages or leaves) respectively, but still do not solve from the freezing problem that stripper loop begins.
On the other hand, invention disclosed provides in day disclosure special permission 61-36197 number, and crucible is separated ring separately, and stay-warm case only is configured in the top of raw material melting area periphery to increase the melting area temperature and to quicken melting raw materials thus.Yet this invention only is used as the insulation of raw material melting area, and the stripper loop inboard was cooled and begins coagulation problem from stripper loop thus and do not solve during silicon single-crystal drew.
If one side is simultaneously pulled out monocrystalline to crucible supply grain silicon continuously and directly, will run into following difficulty:
(1) drawing during the silicon single-crystal when melt temperature reaches cardinal principle near the fusing point of silicon, if under this condition, temperature is added continuously the outside of stripper loop near the grain silicon of room temperature, then grain silicon no longer melts, therefore solid granulates silicon swims in bath surface like this, and melt serves as to examine to solidify and grow up with this grain silicon just.
(2) pull out the district when being separated out when grain silicon melting area and monocrystalline, because so-called " radiator element effect " and heat emissivity coefficient are than silicon melt height, solidification is tended to take place from this partition part, like this in case solidify, solidify material and grow up continuing, the growth of zero defect silicon monocrystalline is hindered.
The objective of the invention is to overcome the problems referred to above that exist in the prior art, main purpose of the present invention provides the method and apparatus of preparation silicon single-crystal, by supply with particulate state or fritter shape raw silicon continuously to the crucible that fused raw material is housed, guarantee that in crucible particulate state or little bulk silicon raw material are melted to prevent that liquid from solidifying and not hindering the growth of silicon single-crystal from partition part, preparation has concentration of dopant and oxygen concn at the constant substantially silicon single-crystal of pull-out direction thus.
For this reason, according to the present invention, a kind of preparation method of silicon single-crystal is provided, single crystal growing district and outer fueled zone in the crucible that wherein fills molten silicon is separated into so that molten silicon move slowly, and one side adds the silicon raw material continuously, one side draws out silicon single-crystal from the single crystal growing district, and present method has following characteristics:
(1) fusing point that remains on than silicon of the temperature of charging zone and molten silicon exceeds more than 12 ℃ at least.
(2) in the method, provide lagging material to cover dividing plate and expose from the melting charge surface part and cover charging zone one side of dividing plate.
(3) substantially the annular well heater top that is placed in charging zone top and dividing plate is covering them, and the heating maintenance dividing plate by this well heater and the temperature of charging zone molten silicon are higher than the temperature of single crystal growing district molten silicon.
(4) molten silicon in the crucible is by being placed in the heater heats of crucible outside, and meanwhile the molten silicon in charging zone is by being placed in the heater heats in the charging zone, and its mode is that the part well heater is immersed in the molten silicon of charging zone.
(5) in above-mentioned (1) in (4), the molten silicon in crucible by being placed in the crucible periphery well heater and be placed in heater heats below the crucible.
(6) and then in above-mentioned (1) in (5), contact area in charging zone between molten silicon and the crucible is configured in whole crucible the 30-75% of contact area between the molten silicon and crucible, and the free area of molten silicon is configured to the 10-70% of molten silicon free area in whole crucible in charging zone.
According to the present invention, the equipment of realizing aforesaid method also is provided, in order to draw silicon single-crystal from the crucible molten silicon, this equipment has following characteristics:
(1) provides a kind of isolation board device that has at least an aperture to pass through, it is placed in the crucible inner loop around the silicon single-crystal that is drawn out, and crucible is separated into single crystal growing district and charging zone, the grain silicon feeder is placed in the charging zone top, attemperator covers the part that dividing plate exposes from bath surface and covers charging zone, and the well heater of heating crucible sidewall and bottom respectively.
(2) provide and had the isolation board device that at least one aperture passes through, and be placed in crucible inside crucible is separated into single crystal growing district and charging zone, the grain silicon feeder is placed in the charging zone top, substantially the annular well heater is placed in top charging zone and dividing plate covering them, and the well heater of heating crucible sidewall and bottom respectively.
(3) provide and had the isolation board device that at least one aperture passes through, it is positioned in crucible inside to be separated into single crystal growing district and charging zone around the silicon single-crystal that is drawn with crucible, be placed in the grain silicon feeder of charging zone top, mounting means is immersed in the charging zone molten silicon for part but also can be with respect to the well heater of crucible vertical movement, and the well heater of heating crucible sidewall.
(4) provide cylinder heater, it is positioned in the crucible and forms the slit around the silicon single-crystal that is drawn and with crucible bottom, and crucible is separated into single crystal growing district and charging zone, and the grain silicon feeder that is placed in the charging zone top.
(5) in above-mentioned (1) in (4), molten silicon and contact area between crucible are configured to contact between molten silicon and crucible the 30-75% of area in whole crucible in charging zone, and the free area of molten silicon is configured to the 10-70% of molten silicon free area in whole crucible in charging zone.
Fig. 1 is the longitudinal section view of expression one embodiment of the invention.
Fig. 2 is the cross section view along Fig. 1 I-I line.
Fig. 3 is the side-view of an embodiment of expression dividing plate.
Fig. 4 is the side-view that has local section of an embodiment of expression warming plate.
Fig. 5 is the chart that concerns between the above temperature rise of expression grain silicon fusing time and silicon fusing point.
Fig. 6 to Figure 11 is respectively the longitudinal section view and their II-II, III-III and the IV-IV sectional view of other embodiments of the present invention.
Figure 12 is the skeleton view of an embodiment of expression cylinder heater.
Figure 13 be illustrated in melt contact area charging zone and in whole crucible and bath surface long-pending between the curve of relation.
Figure 14 (a) and (b) represent the longitudinal section view and the vertical view of dividing plate embodiment respectively.
The description of optimum implementation
Fig. 1 is the longitudinal section view of expression one embodiment of the invention, and Fig. 2 is the sectional view along Fig. 1 I-the I line is got.Number in the figure 1 expression quartz crucible, it is contained in plumbago crucible 2 the insides, and plumbago crucible 2 be bearing in can the also rotary bearing 3 of vertical movement on, label 4 expressions are contained in the melting charge in the crucible 1, grow into columniform silicon single-crystal 5 and pull out from melting charge.Label 6 expressions center on the well heater of plumbago crucible 2, and the 7th, around the hot-zone lagging material of well heater 6.These members all are placed in the body of heater 8, and to prepare the conventional equipment of silicon single-crystal identical with Czochralski method basically for they.
A perforate on the label 9 expression bodies of heater 8, it is corresponding with the bath surface of charging zone B, insert feeder 13 regularly in order to add particulate state or bulk silicon raw material (hereinafter being called grain silicon) in perforate 9, the front end of feeder 13 is facing to the bath surface of charging zone B.Feeder 13 is connected with the feed compartment (not shown) that is placed in body of heater 8 outsides, adds grain silicon 16 for continuously thus charging zone B.
Label 17 expression warming plates, it is made up of high-intensity graphite cake, as shown in Figure 4.Be noted that from the viewpoint that prevents to stain surface, the lower of this graphite cake or whole surface preferably cover one deck, the high-purity quartz of for example about 3 mm thick, perhaps high-purity carborundum (SiC) or silicon nitride (Si
3N
4) top coat.The neighboring of warming plate 17 is fixed on the hot-zone heat insulating element 7, and makes it surround dividing plate 11 and charging zone B.Warming plate 17 is installed in this manner, though its bottom (inside circumference) near bath surface (being about 10 millimeters) at the present embodiment middle distance thus prevent that melting charge from solidifying and improve heat insulation effect for melt in charging zone B in the part that dividing plate 11 exposes in melt.Label 18 expression corresponding holes, a visual field with Temperature Detector 14, the 19th, be positioned at a hole on the feeding-passage of grain silicon 16.
According to the present invention well heater 20(it be what to separate with well heater 6) be placed in the bottom of plumbago crucible 2, and crucible 1 places in the crucible 2, controls the bath surface temperature of single crystal growing district A and charging zone B thus reliablely.By regulating well heater 6 and 20, grain silicon 16 can be melted in charging zone B reliably and the melt in single crystal growing district A can maintain the temperature under the situation that does not influence silicon monocrystal growth.
In embodiment of the present invention as described above, melting charge 4 is included in the inboard and the outside of the dividing plate 11 that places crucible 1, and the liquid level of these melts remains on identical height.When seed crystal in single crystal growing district A with after bath surface contacts, seed crystal rotated lentamente and,, so just produce cylindrical silicon monocrystalline 5 along with crystal growth takes place solidifying of liquid level of contact simultaneously by pulling out in the melt.Around here, grain silicon 16 is entered the bath surface of charging zone B continuously by feeder 13, grain silicon 16 is melted by melt at charging zone B like this, and it flows into single crystal growing district A lentamente by the aperture on the dividing plate 11 12, keeps the liquid level of melting charge 4 constant all the time thus.Like this, can prevent by dividing plate 11 owing to add any fluctuation that grain silicon 16 causes to bath surface at charging zone B, also without any wave propagation to single crystal growing district A.
The low side of feeder 13 is placed in the bath surface top makes grain silicon 16 fall into bath surface, and this true purpose is that grain silicon 16 is swum on whole bath surfaces of charging zone B, and it is melted in the whole zone of charging zone B.If the front end of feeder 13 is immersed in the melt, then the melting range of grain silicon 16 is limited in filling tube inside, so just causes being passed to by melt the shortage of heat of grain silicon 16, and grain silicon 16 can not be melted continuously.
For above-mentioned embodiment, must give below the diameter of the aperture 12 on dividing plate 11 and the number to consider.If the diameter of aperture 12 is excessive or its number is too much, then can between single crystal growing district A and charging zone B, cause melt convection.That is to say that low-temperature melt in single crystal growing district A flows into charging zone B, be difficult to fusing point that the melt temperature of maintenance charging zone B is higher than silicon like this more than 12 ℃, as the back will as described in.In the present embodiment, the diameter of aperture 12 is 5 millimeters, and little number of perforations is 2.
The test-results of temperature measuring shows, for pulling out zero defect silicon monocrystalline 5, causes melt solidifying when preventing from simultaneously to add grain silicon 16 continuously and prevents and around dividing plate 11 melt solidifyings take place, must be higher at least 12 ℃ than the fusing point of silicon at the melt temperature of charging zone B; As shown in Figure 5.For this reason, according to the present invention, it is to solidify around dividing plate 11 in order to prevent that warming plate 17 is provided, and is the thermal radiation of minimizing at the melt of charging zone B, thereby guarantees heat insulation effect; In addition, settle well heater 6 and 20 in the outside of plumbago crucible 2, with the fusing that guarantees grain silicon 16 in quartz crucible 1 simultaneously and the growth of silicon single-crystal 5.In other words, well heater 6 is placed in the side of crucible 1 and the bottom that well heater 20 is placed in crucible 1, their performance effects separately, be that the former makes grain silicon 16 fusings that enter charging zone B, the latter regulates the temperature of single crystal growing district A, and one side is measured two bath surface temperature respectively with Temperature Detector 14 and 15 and simultaneously controlled single crystal growing temperature and grain silicon temperature of fusion (fusing point than silicon is high at least more than 12 ℃) respectively with well heater 20 and 6.
Fig. 6 is the longitudinal section view of expression another embodiment of the present invention, and Fig. 7 is the cross section view along Fig. 6 II-the II line is got.The difference of the present embodiment and Fig. 1 embodiment is, the top that well heater 21 is placed in charging zone B and dividing plate 11 is so that cover them, and it comprises, for example the cardinal principle annular graphite heating element of resistive heating type.During loading raw silicon, top or crucible 1 that well heater 21 is moved upward to crucible move down so that feed.Equally, when raw silicon melted, well heater 21 moved down or crucible moves up.The part of well heater 21 (being positioned at the top of charging zone B) is given melt 4 heating of charging zone B, and the another part that is positioned at dividing plate 11 tops is given the top firing of dividing plate 11 by radiant heat.Well heater 21 can comprise nichrome wire or the identical analogue of effect.Should be pointed out that the warming plate 17 that in the present embodiment, does not need as shown in Fig. 1 embodiment.
In the present embodiment, by control heater 6 and well heater 21 bath surface of charging zone B and the top of dividing plate 11 are kept at high temperature, the melt temperature of charging zone B remain on be higher than silicon fusing point below at least 12 ℃ to guarantee grain silicon 16 fusing, and prevent to solidify from dividing plate 11 at single crystal growing district A, thereby being remained on, melt do not influence under the temperature of silicon single-crystal 5 growths.
Fig. 8 is the longitudinal section view of expression another embodiment of the present invention, and Fig. 9 represents along the cross section view that Fig. 8 III-the III line is got.Except that well heater 22, this embodiment is identical with the embodiment of Fig. 1.Well heater 22 includes, resistance heating element for example, and it is processed to the shape of a hoof substantially, and its section is L shaped, and surface coverage is with highly purified silica glass or analogue.During loading raw silicon, top or crucible that well heater 22 is moved upward to crucible move down so that reinforced, and when raw silicon melts, well heater 22 moves down or crucible moves up, so that well heater is immersed in the melt 4 of outside charging zone B of dividing plate 11 to substantially in the middle part of vertical direction.Well heater 22 is immersed in melt 4 heating that the part in the melt 4 is given charging zone B, and the part that does not immerse melt 4 is given the top firing of dividing plate 11 by radiant heat.Should point out, in the present embodiment, remove the well heater 20 that is placed under the crucible 1.
In the present embodiment, by control heater 22 and well heater 6, the fusing point that the melt temperature of charging zone B is remained on be higher than silicon is more than at least 12 ℃, make the reliable fusing of grain silicon and in single crystal growing district A melt remain under the temperature that does not influence silicon single-crystal 5 growths.
About Figure 10 and Figure 11, Figure 10 is the longitudinal section view of expression yet another embodiment of the invention, and Figure 11 is the cross section view that IV-the IV line is got along Figure 10.The present embodiment is that with the different of Fig. 1 embodiment the present embodiment provides a cylinder heater 23, it be by, for example the resistance heating element that coats with high-purity quartz glass is formed (as shown in figure 12).Cylinder heater 23 and crucible 1 concentric placement make the temperature of its neighboring heating be higher than its inner circumference.During loading raw silicon, cylinder heater 23 moves up or crucible 1 moves down so that reinforced, and when raw silicon melted, cylinder heater 23 moves down or crucible moves up was immersed in the melt 4 well heater 23, and some is exposed to make it.At this moment, crucible 1 is separated into single crystal growing district A and charging zone B, be heated to temperature at the lateral melt of the charging zone of cylinder heater 23 and be higher than the lateral melt temperature of single crystal growing district A, by moving to single crystal growing district A lentamente at the slit melt of crucible 1 than lower part.
In the present embodiment, by control cylinder heater 23 and well heater 6, it is higher at least more than 12 ℃ than silicon fusing point that the temperature of charging zone B melt is remained on, and grain silicon reliably melted, and also remain under the temperature that does not influence silicon monocrystal growth at the melt of single crystal growing district A.
In addition, in the preparation method of this class silicon single-crystal that simultaneously adds a growing single-crystal of raw material, basic requirement is that the grain silicon fusing that is added will reliably and not can cause any disastrous effect, for example can not cause any temperature variation in silicon monocrystal growth district.For this purpose, it is an effective means that crucible is separated into charging zone and single crystal growing district, if but this separation is inappropriate, and the result who then obtains can be not satisfactory, as the front was described with example about prior art.When dividing plate placed crucible that crucible is separated into charging zone and single crystal growing district, the motion of heat was such in charging zone, and promptly heat is basically from the contact surface (S between melt and crucible
BS) discharge, and heat exhaustion is in the grain silicon of fusing adding.Therefore, if contact surface (S
BS) increase, then the heat input also increases, and this is favourable for the fusing grain silicon.Yet, if contact (S
BS) increase excessively, then the heat for the input of crystal growth district is reduced, and like this problem will take place.In contrast, if free area (S
BS) reduce, then quantity of heat given up reduces, and this also is favourable from the viewpoint of material melting.
Inventor of the present invention tests and studies according to above-mentioned notion, and successfully crucible is separated to guarantee area S
TSAnd S
TSSuitable, make the grain silicon fusing reliable thus.
In addition, according to the temperature measuring test-results, the temperature of discovery melt in charging zone B must be higher at least more than 12 ℃ than the fusing point of silicon, as shown in Figure 5, so that draw out flawless silicon single-crystal, and prevent from simultaneously melt solidifying to take place and prevent to solidify (as noted above) around the dividing plate owing to adding grain silicon continuously.For this reason, obtained segregation method by test in the present embodiment, this method can prevent to solidify and the grain silicon of adding is reliably melted in the part that dividing plate exposes from melt, and the melt temperature pointed out above of assurance.
Figure 13 has provided this result.Have been found that for melt grain silicon and in single crystal growing district A growing silicon single crystal, crucible must be separated in such a way, though in charging zone B the area (S of the contact part of melt and crucible 1
TS) be configured to the area (S of melt and crucible 1 contact part in whole crucible
S) 30-75%, make the free area (S of melt in charging zone B
TS) be the free area (S of whole melts in whole crucible
TS) 10-70%(note: S
TS/ S
TSThe lower limit of ratio is to determine according to add the required minimum space of grain silicon to bath surface).If S
TS/ S ratio is big, and S
BS/ S
BSRatio is too small, and then charging zone B can not guarantee desired melt temperature (fusing point that is higher than silicon is more than 12 ℃).On the other hand, if S
S/ S
7Ratio is little, and S
BS/ S
BRatio is too small, then melt solidifying in single crystal growing district A.Therefore, satisfy above-mentioned ratio S
BS/ S and S
B/ S
BOr the separation condition is unique requirement of dividing plate 11 typings.
The longitudinal section shape and the shape of cross section of applied typical diaphragm 11 during Figure 14 represents to test.Longitudinal section shape and shape of cross section combined to obtain difform dividing plate 11, when reality adds grain silicon, successfully drawn out silicon single-crystal by using these dividing plates 11.
In above-mentioned embodiment, use single feeder 13 to add granular silicon feedstock 16 to the bath surface of charging zone B continuously, two or more feeders 13 also can be provided.Should be pointed out that the grain silicon 16 that is added includes doping agent, its amount is consistent with the content in drawing silicon single-crystal, because this point is for being matter of course with the method that adds grain silicon drawing silicon single-crystal, so the front was not described.Therefore, the concentration of dopant of melt equates with the concentration of dopant of the silicon single-crystal of drawing in charging zone.In addition, verified, the present invention even also can carry out satisfactorily outer applying under the situation in magnetic field in the face of melt from body of heater 8.
From above description as can be seen, can draw out flawless silicon single-crystal according to the present invention, the characteristics of its structure are: crucible is separated into inner region and outskirt by isolation board device adds grain silicon to give the charging zone bath surface continuously, thereby the grain silicon that is added is melted and moves to the single crystal growing district and keeps the liquid level of molten silicon constant and eliminate temperature variation and change in concentration simultaneously like this, by adopting warming plate and two well heaters, ring heater element or L shaped plus heater element or the fusing point that replaces measure such as dividing plate that the temperature of charging zone melt is remained on conversely being higher than silicon with cylinder heater be more than at least 12 ℃, even also prevented the propagation of wave to the single crystal growing district when charging zone adds grain silicon continuously.
So, work of the present invention has very big effect, by guaranteeing to improve productivity acquisition raising or the like even production of pull-out direction quality.
Be noted that by being adjusted at the contact area (S between charging zone melt and the crucible
BS) be the contact area (S between melt and the crucible in whole crucible
B) 30-75% and the free area (S that is adjusted at the charging zone melt
TS) be the free area (S of whole melts in whole crucible
T) 10-70% will obtain bigger effect.
Claims (9)
1, a kind of preparation method of silicon single-crystal, comprising: single crystal growing district and outer fueled zone in the crucible that will fill molten silicon is separated into so that the molten silicon motion slowly, and one add silicon raw material one side continuously towards charging zone and pull out silicon single-crystal by the single crystal growing district, wherein improves the temperature that comprises charging zone and molten silicon and remain on the fusing point more than at least 12 ℃ that is higher than silicon;
Provide attemperator to cover dividing plate and expose from molten silicon surface part and charging zone one side of described dividing plate; And
The contact area of molten silicon and crucible is configured to the 30-75% of the contact area of molten silicon and crucible in whole crucible in charging zone, and the free area of molten silicon is configured to the 10-70% of the free area of molten silicon in whole crucible in charging zone.
2, according to the preparation method of claim 1, the temperature of wherein said dividing plate and charging zone molten silicon remains on the temperature that is higher than single crystal growing district molten silicon by being placed in charging zone and dividing plate top with the heating of the cardinal principle annular well heater that covers both.
3, according to the preparation method of claim 1, wherein the molten silicon in the crucible is with the heater heats that is placed in described crucible outside, and wherein the molten silicon in the charging zone with another heater heats (its mode is immersed in the molten silicon of charging zone for the part well heater) that is placed in the charging zone.
4, according to the preparation method of claim 1, wherein the molten silicon in crucible is with the well heater that is placed in the crucible outside and be placed in another heater heats below the crucible.
5, according to the preparation method of claim 1, wherein improvement comprises step:
With cylinder heater the molten silicon in the crucible is separated into two portions, makes this well heater surround the silicon single-crystal of from molten silicon, pulling out;
With the molten silicon in another heater heats crucible that is placed in the crucible outside;
Mainly heat at the molten silicon in this cylinder heater outside with cylinder heater and to be higher than the fusing point of silicon more than at least 12 ℃ with the melt temperature of the molten silicon that remains on this cylinder heater outside;
Pull out silicon single-crystal from the inboard of cylinder heater; With
The outside at cylinder heater adds grain silicon; With
The molten silicon in the cylinder heater outside is by its beneath interior lateral movement to cylinder heater.
6, produce a kind of silicon single-crystal of silicon single-crystal and prepare equipment by pulling out the molten silicon that is contained in the crucible, wherein improve and comprise: have the dividing plate of at least one through hole, this dividing plate is placed in and makes it surround the silicon single-crystal of pulling out in the crucible from crucible and make crucible be separated into single crystal growing district and charging zone; Be placed in the grain silicon feeder of described charging zone top; In order to cover the part that described dividing plate exposes from molten silicon surface and the attemperator of charging zone; With the well heater at the bottom of difference heating crucible sidewall and the crucible; And wherein in charging zone the contact area of molten silicon and crucible be configured to the 30-75% of molten silicon and crucible contact area in whole crucible, and wherein in charging zone the free area of molten silicon be configured to the 10-70% of molten silicon free area in whole crucible.
7, according to the preparation equipment of claim 6, wherein improvement comprises:
Dividing plate with at least one small through hole, this dividing plate are placed in and make crucible be separated into single crystal growing district and charging zone in the crucible;
Be placed in the grain silicon feeder of charging zone top;
Be placed in charging zone and dividing plate top to cover both cardinal principle annular well heaters; With
Well heater at the bottom of difference heating crucible sidewall and the crucible.
8, according to the preparation equipment of claim 6, wherein improvement comprises:
Dividing plate with at least one small through hole, this dividing plate are placed in and make it surround the silicon single-crystal of pulling out in the crucible from crucible and make crucible be separated into single crystal growing district and charging zone;
Be placed in the grain silicon feeder of charging zone top;
Be placed in the well heater of charging zone inside, its part is immersed in the molten silicon of charging zone, described well heater can be done vertical movement with respect to crucible; With
Another well heater of heating crucible sidewall.
9, according to the preparation equipment of claim 6, wherein improvement comprises:
The cylinder heater that is placed in the crucible surrounds the silicon single-crystal of pulling out from molten silicon, make between this well heater and the crucible bottom and form the slit, and crucible is separated into single crystal growing district and charging zone; With
Be placed in the grain silicon feeder of charging zone top.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63104278A JPH01275495A (en) | 1988-04-28 | 1988-04-28 | Production of silicon single crystal and device therefor |
| JP104278/88 | 1988-04-28 | ||
| JP112614/88 | 1988-05-11 | ||
| JP130269/88 | 1988-05-30 | ||
| JP131653/88 | 1988-05-31 | ||
| JP63208446A JPH0259494A (en) | 1988-08-24 | 1988-08-24 | Production of silicon single crystal and apparatus |
| JP208446/88 | 1988-08-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1037933A CN1037933A (en) | 1989-12-13 |
| CN1016973B true CN1016973B (en) | 1992-06-10 |
Family
ID=26444785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89102980 Expired CN1016973B (en) | 1988-04-28 | 1989-04-28 | Method and apparatus for manufacturing silicon single crystals |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1016973B (en) |
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|---|---|---|---|---|
| CN113061978A (en) * | 2021-03-22 | 2021-07-02 | 上海引万光电科技有限公司 | Molten silicon feeder for continuous Czochralski single crystal pulling |
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|---|---|---|---|---|
| US10358740B2 (en) * | 2014-07-25 | 2019-07-23 | Corner Star Limited | Crystal growing systems and methods including a passive heater |
| CN104499048A (en) * | 2014-12-07 | 2015-04-08 | 海安县石油科研仪器有限公司 | Monocrystalline silicon growth process based on continuous feeding |
| CN106242295B (en) * | 2016-07-15 | 2019-02-01 | 江西科盛环保股份有限公司 | The anti-squama burst porcelain glaze of Q345 hot rolled alloy steel counterenamel and function overglaze |
| CN108298819B (en) * | 2018-02-08 | 2020-07-10 | 赵庭玉 | High-temperature porcelain glaze for high-chromium white cast iron |
| CN108249762A (en) * | 2018-03-23 | 2018-07-06 | 深圳市金合联供应链技术有限公司 | A kind of grate high acid-proof cast iron Enamel Slip and preparation method thereof |
| CN110735180A (en) * | 2018-07-20 | 2020-01-31 | 上海新昇半导体科技有限公司 | crystal pulling furnace |
| CN108821587B (en) * | 2018-08-14 | 2021-10-15 | 南京双峰油泵油嘴有限公司 | Formula and process of industrial enamel for cast iron |
| CN113373518B (en) * | 2021-07-16 | 2023-05-30 | 山东恒元半导体科技有限公司 | Device and method for growing oversized long-constant-diameter lithium niobate |
-
1989
- 1989-04-28 CN CN 89102980 patent/CN1016973B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061978A (en) * | 2021-03-22 | 2021-07-02 | 上海引万光电科技有限公司 | Molten silicon feeder for continuous Czochralski single crystal pulling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037933A (en) | 1989-12-13 |
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