CN102898034A - Method for manufacturing silicon nitride coating of crucible for crystalline silicon ingot casting - Google Patents
Method for manufacturing silicon nitride coating of crucible for crystalline silicon ingot casting Download PDFInfo
- Publication number
- CN102898034A CN102898034A CN2012103693258A CN201210369325A CN102898034A CN 102898034 A CN102898034 A CN 102898034A CN 2012103693258 A CN2012103693258 A CN 2012103693258A CN 201210369325 A CN201210369325 A CN 201210369325A CN 102898034 A CN102898034 A CN 102898034A
- Authority
- CN
- China
- Prior art keywords
- silicon nitride
- crucible
- nitride coating
- silicon
- zone
- 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.)
- Granted
Links
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 199
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 238000000576 coating method Methods 0.000 title claims abstract description 150
- 239000011248 coating agent Substances 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000005266 casting Methods 0.000 title claims abstract description 45
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 46
- 239000010703 silicon Substances 0.000 claims abstract description 46
- 238000000280 densification Methods 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000001764 infiltration Methods 0.000 claims description 32
- 230000008595 infiltration Effects 0.000 claims description 27
- 238000012545 processing Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 230000000694 effects Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- 238000005245 sintering Methods 0.000 abstract description 10
- 238000000151 deposition Methods 0.000 abstract description 7
- 230000006378 damage Effects 0.000 abstract description 5
- 239000000428 dust Substances 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000005507 spraying Methods 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000013078 crystal Substances 0.000 description 8
- 239000005350 fused silica glass Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 5
- 229920005591 polysilicon Polymers 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a method for preparing a silicon nitride coating of a crucible for a crystalline silicon ingot casting, which comprises the steps of preparing the silicon nitride coating in an easily-adhered crucible region on the inner wall of the crucible by adopting a liquid phase deposition method, then carrying out densification and non-wetting treatment on the silicon nitride coating in the region, preparing the silicon nitride coating in other regions on the inner wall of the crucible by adopting the liquid phase deposition method, and finally baking the silicon nitride coating at low temperature or carrying out non-sintering treatment on the silicon nitride coating to obtain the silicon nitride coating of the crucible for the crystalline silicon ingot casting. The method can obviously improve the overall strength of the silicon nitride coating, particularly improve the strength of the coating in the area easy to adhere to the crucible and the non-wettability of the coating to silicon melt, effectively avoid the phenomenon of crucible adhesion, avoid the generation of silicon nitride dust, further improve the effective utilization rate of the silicon nitride powder, reduce the production cost, enhance the environmental friendliness in the operation process and reduce the harm to the human body; and because low-temperature baking is not needed or only needed, the waste of energy is reduced, and the production period is shortened.
Description
Technical field
The invention belongs to technical field of solar cells, be specifically related to a kind of making method of crystalline silicon crucible for casting ingots silicon nitride coating.
Background technology
In the crystalline silicon ingot casting is produced, silicon nitride coating plays isolated silicon melt and fused silica crucible, thereby play stop the intrinsic impurity of crucible in the silicon material diffusion and pollute the silicon material, thereby guaranteeing simultaneously that silicon ingot and crucible do not stick together realizes the vital role of the smooth demoulding, thereby essential in crystalline silicon ingot casting Nitrogen During SiClx coating.
For the crystalline silicon ingot casting, silicon nitride coating different zones environment of living in is different, as shown in Figure 1, wherein silicon liquidus position is solid, liquid, gas three-phase junction region, the matrix of silicon melt and silicon nitride coating herein, the reacting phase of fused silica crucible is to the strongest, while silicon nitride coating herein also is subject to the erosion of silicon liquid fluctuation, and the silicon liquidus rises gradually in the process of silicon crystal growth, silicon nitride coating is produced certain physical impact, thereby silicon nitride coating herein the most easily peels off inefficacy.Wherein most important influence factor is the level of response of silicon melt and fused silica crucible, and there is interactional relation in this reaction with the density of silicon nitride coating herein.
Thereby the density that how to strengthen this regional silicon nitride coating is one of key that solves sticking crucible problem.
For the standby silicon nitride coating of spray sintering legal system that conventional ingot casting adopts usually, its drawback realizes and easily sees: in the spraying operating process, relatively a part of silicon nitride powder runs off with air draft, not only cause the waste of silicon nitride powder but also caused the pollution of environment, and the sintering temperature about 1100 ℃ needs a large amount of electric energy and working time, thereby demands urgently improving.
Seen at present the correlative study report of realizing that by in Silicon Nitride, introducing binding agent the silicon nitride coating early strength improves both at home and abroad, in silicon nitride coating, introduce PVA as membrane-forming agent such as people such as R.Einhaus, experimental study with spraying preparation silicon nitride coating, but because the destruction of non-infiltration between silicon nitride coating and silicon melt, cause the silicon ingot cracking, as shown in Figure 2.
Be that report adopts spraying method to prepare the report of non-sintered silicon nitride coating with polyvinyl alcohol, polyacrylic acid etc. as bonding in 201110258563.7 the patent according to another application number, but the silicon nitride coating intensity that experimental results show that the method preparation is relatively poor, and sticking crucible phenomenon seriously can't normally be used.
In sum, improve at present silicon nitride coating intensity and remain the important topic in this area, although currently seen the research that improves coating film forming properties and early strength by the method for introducing binding agent, but because uncontrollable organism still can't be used for actual production at present on the impact of coating non-infiltration; And Patents is mentioned the method for using binding agent in spraying process, owing to fundamentally not improving the particle alignment structure, can't fundamentally improve the intensity of silicon nitride coating.
Summary of the invention
Technical problem to be solved by this invention provides a kind of making method of crystalline silicon crucible for casting ingots silicon nitride coating, the method can be avoided the generation of silicon nitride coating dust in spraying process, further improve the effective rate of utilization of silicon nitride powder, reduce the consumption of silicon nitride powder, thereby reduce production costs; Owing to avoiding the generation of dust, strengthen the environment friendly in the operating process simultaneously, reduced the injury to human body; Density and the non-infiltration of the silicon nitride coating that makes are strong, are difficult for sticking crucible, and the silicon ingot of making is good.
Above-mentioned technical problem of the present invention is achieved by the following technical solution: a kind of making method of crystalline silicon crucible for casting ingots silicon nitride coating, adopt the method for liquid deposition after the easily sticking crucible zone of crucible inwall makes silicon nitride coating, this zone silicon nitride coating is carried out densification and non-infiltration processing, and adopt the method for liquid deposition to make silicon nitride coating in other zone of crucible inwall, at last silicon nitride coating is carried out low-temperature bake or non-sintered processing, obtain crystalline silicon crucible for casting ingots silicon nitride coating.
The easily sticking crucible zone of crucible inwall of the present invention is mainly rib, the angular zone of silicon liquidus zone and the crucible inside of crucible.
The mode that the present invention makes silicon nitride coating is: directly Silicon Nitride is coated on the easily sticking crucible zone of crucible inwall or other is regional, by the silicon nitride particle autodeposition, Silicon Nitride is coated the inwall of crucible, also be referred to as liquid phase deposition.
Be compared to and usually adopt the mode of gas atomization to spray in the prior art, the present invention adopts the mode of above-mentioned liquid deposition, can better Silicon Nitride be coated the easily sticking crucible zone of crucible, and the porosity of the silicon nitride coating of coating is low, and intensity is high.
As a rule, the mode of coating Silicon Nitride is substantially by following several: brush, roller coat, spraying and cast etc., mostly adopt the mode of gas atomization to spray in the prior art, in fact, the porosity of the silicon nitride coating that the mode of employing brushing and roller coat makes will be much smaller than the mode of spraying and cast, comparatively speaking, the method of brushing will be got well than the method for roller coat, the method that the method for roller coat sprays will be got well, spraying is better than again the mode of pouring into a mould, the silicon nitride coating that the mode that employing is brushed obtains is finer and close, the present invention adopts the mode of brushing to the silicon nitride coating in the easily sticking crucible zone of crucible inwall, for other zone of crucible inwall, spraying is adopted in the place not too high to the requirement of silicon nitride coating, roller coat and cast or two kinds of modes that combine wherein.
Silicon Nitride of the present invention by alpha-silicon nitride powders, pure water and binding agent by weight than being that 100:70 ~ 450:0.1 ~ 15 are formulated.
Binding agent of the present invention is one or more in methyl methacrylate, vinylformic acid, polyvinyl alcohol and the colloid silica.
Densification of the present invention is: in the drying process of the easily Silicon Nitride in sticking crucible zone of crucible, by stirring, vibration or extrusion machinery effect make crucible easily the silicon nitride particle in sticking crucible zone be densification and arrange, obtain the densification silicon nitride coating.
Non-infiltration of the present invention is treated to surface finish, polishing and adsorption dry silicon nitride powder is carried out in the silicon nitride coating surface of densification, obtains the non-infiltration silicon nitride coating.So-called non-infiltration namely is in the ingot casting process of silicon crystal, the silicon material of melting is difficult for entering in the silicon nitride coating, by the non-infiltration processing, can improve the non-infiltration between silicon melt and the silicon nitride coating, prevent the generation of sticking crucible phenomenon, and guarantee the purity of silicon crystal.
Definition about non-infiltration, non-infiltration and wetting property are relative indexs, refer to that mainly liquid is to the wetness degree of solid, its main standard is for infiltrating the size at angle, as shown in Figure 7, for silicon melt (liquid) and silicon nitride coating (solid), when non-infiltration between the two refers to silicon melt and silicon nitride coating Surface Contact, the size of the angle between liquid edge and the silicon nitride coating, this angle larger (＞90 °) illustrates that the two non-infiltration is better, otherwise, if the two angle is less, non-infiltration poorer (shown in the C among Fig. 7) between the two is described.For silicon nitride coating, non-infiltration is the bigger the better between the two, can separate fully with coating after silicon melt solidifies like this, and if mutually infiltrate between the two, that is to say the non-infiltration reduction, then probably cause sticking crucible.
The silicon nitride coating that adopts the method among the present invention to prepare, because porosity is low, intensity is good, so do not need sintering, when toasting such as need, the temperature when low-temperature bake of the present invention is processed is for being lower than 500 ℃; Need to the sintering temperature about 1100 ℃ compare with conventional silicon nitride coating, sintering temperature has reduced nearly 600 ℃.
The present invention has following advantage:
(1) the present invention carries out densification by the silicon nitride coating in the sticking crucible zone of commute (mainly referring to the silicon liquidus), and the silicon nitride coating of acquisition can reduce more than 40% with respect to the porosity of the silicon nitride coating that traditional method such as spraying method make; Aspect intensity, the intensity of the silicon nitride coating of the present invention's preparation improves one to two grade, and especially sintering Front-coating mirror intensity is significantly improved, and can greatly lower the coating damage that collides with and cause because of the silicon material in the charging process, and concrete hardness performance sees the following form 1;
Table 1 different methods prepares the silicon nitride coating pencil hardness test
(2) silicon nitride coating for preparing of the present invention only needs low-temperature bake below 500 ℃ to use;
(3) silicon nitride coating that adopts the method among the present invention to obtain glues the ratio of crucible phenomenon under can the conditions such as accurate monocrystalline ingot casting that the significantly reduce temp gradient is large, long crystal bar spare is harsh, substantially stops the sticking crucible phenomenon in the polycrystalline cast ingot;
(4) adopt the inventive method to prepare silicon nitride coating, can avoid the generation of silicon nitride dust in spraying process, from the effective rate of utilization of further raising silicon nitride powder, reduce the consumption of silicon nitride powder, thereby reduce production costs; Owing to avoiding the generation of dust, strengthen the environment friendly in the operating process simultaneously, reduced the injury to human body;
(5) adopt the inventive method to prepare silicon nitride coating, can greatly shorten the production cycle, reduce energy consumption, reduce production costs.
Description of drawings
The silicon liquidus position that solid, liquid, gas three-phase junction region formed in the crucible when Fig. 1 was silicon material fusing of the present invention;
Fig. 2 is the diagram of the silicon crystal that forms when adopting crucible with silicon nitride coating in the prior art to carry out ingot casting;
Fig. 3 is the making processes schematic diagram of silicon nitride coating in the crucible of the present invention;
Contrast schematic diagram when Fig. 4 is the crucible of the employing embodiment of the invention 1 silicon nitride coating and the crucible ingot casting polysilicon that adopts conventional silicon nitride coating;
Contrast schematic diagram when Fig. 5 is the crucible of the employing embodiment of the invention 2 silicon nitride coatings and the crucible ingot casting silicon single crystal that adopts conventional silicon nitride coating;
Contrast schematic diagram when Fig. 6 is the crucible of the employing embodiment of the invention 3 silicon nitride coatings and the efficient polysilicon of crucible ingot casting that adopts conventional silicon nitride coating;
Fig. 7 is about the schematic diagram of non-infiltration interpretation among the present invention.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing.
Embodiment 1
The making method of the crystalline silicon crucible for casting ingots silicon nitride coating that the present embodiment provides, preparation flow be as shown in Figure 2:
At first, the preparation Silicon Nitride, wherein Silicon Nitride by alpha-silicon nitride powders, pure water and binding agent by weight than being that 100:150:5 is formulated.Wherein binding agent is adopted as methyl methacrylate, vinylformic acid, polyvinyl alcohol, colloid silica, and its mass ratio is 1:1:10:10, and adopts the easily sticking crucible zone of above-mentioned liquid deposition method coating, mainly refers to the silicon liquidus zone of crucible.
Then, the silicon nitride coating that the easily sticking crucible zone of crucible is made carries out densification and non-infiltration processing, and crucible is generally fused silica crucible.Densification is: in the drying process of the easily Silicon Nitride in sticking crucible zone of crucible, the silicon nitride particle that makes crucible easily glue the crucible zone by mechanical effects such as stirring, vibration or extruding is the densification arrangement, obtain the densification silicon nitride coating, it is that the equipment of ZL201120254516.0 carries out that the mechanical effects such as stirring, vibrations and extruding can adopt the patent No., also can adopt miscellaneous equipment to carry out.Non-infiltration is treated to surface finish, polishing and the processing of adsorption dry alpha-silicon nitride powders is carried out in the silicon nitride coating surface of densification, obtains the non-infiltration silicon nitride coating.
Then, other zone preparation silicon nitride coating at the crucible inwall because other zone of crucible inwall is relatively low to density and the requirement of strength of silicon nitride coating, can adopt the mode of cast or cast+roller coat to prepare.
At last, above-mentioned silicon nitride coating is carried out non-sintered (dry and need not baking), namely make obtaining crystalline silicon crucible for casting ingots silicon nitride coating.
After adopting common polycrystalline technique to carry out ingot casting and the demoulding, the polycrystal silicon ingot that obtains as shown in Figure 4, wherein a figure adopts the crucible of conventional silicon nitride coating coating behind 1100 ℃ of sintering among Fig. 4, the picture that is used for the ingot casting polysilicon, b figure is after adopting the non-sintered processing of silicon nitride of the present invention's preparation, the polysilicon picture that is used for ingot casting, as can be seen from Figure 4, significantly sticking crucible appears in the silicon liquid level place among a figure, the crucible disc that diameter surpasses 30mm sticks to the silicon ingot surface, similar sticking crucible situation causes silicon ingot hidden crackle even cracking to occur most probably, the silicon ingot sidepiece adheres to a large amount of alpha-silicon nitride powders simultaneously, this illustrates that this coating is in use less with crucible inwall sticking power, and stability is lower; A small amount of silicon nitride powder is only adhered on the silicon ingot surface among the b figure, and without any sticking crucible zone, silicon ingot separates thoroughly with crucible.This point proof more conventional spraying silicon nitride coating of silicon nitride coating of the present invention adsorptive power on the crucible inwall in the polycrystalline cast ingot demoulding is used is stronger, and demolding performace is more stable.
Embodiment 2
The making method of the crystalline silicon crucible for casting ingots silicon nitride coating that the present embodiment provides, preparation flow be as shown in Figure 2:
At first, the preparation Silicon Nitride, wherein Silicon Nitride by alpha-silicon nitride powders, pure water and binding agent by weight than being that 100:150:10 is formulated.Wherein binding agent is adopted as methyl methacrylate, vinylformic acid, polyvinyl alcohol, colloid silica, and its mass ratio is 0.1:1:10:10, and adopts above-mentioned Silicon Nitride to brush the easily sticking crucible zone of silicon nitride, mainly refers to the silicon liquidus zone of crucible.
Then, the silicon nitride coating that the easily sticking crucible zone of crucible is made carries out densification and non-infiltration processing, and crucible is generally fused silica crucible.Densification is: in the drying process of the easily Silicon Nitride in sticking crucible zone of crucible, by the mechanical effects such as stirring, vibration or extruding make crucible easily the silicon nitride particle in sticking crucible zone be densification and arrange, obtain the densification silicon nitride coating; It is that the equipment of ZL 201120254516.0 carries out that the mechanical effects such as stirring, vibrations and extruding can adopt the patent No., also can adopt miscellaneous equipment to carry out; Non-infiltration is treated to surface finish, polishing and the processing of adsorption dry alpha-silicon nitride powders is carried out in the silicon nitride coating surface of densification, obtains the non-infiltration silicon nitride coating.
Then, other zone preparation silicon nitride coating at the crucible inwall because other zone of crucible inwall is relatively low to density and the requirement of strength of silicon nitride coating, can adopt the mode of cast or cast+roller coat to prepare.
At last, above-mentioned silicon nitride coating is carried out 500 ℃ of baking processing, namely make obtaining crystalline silicon crucible for casting ingots silicon nitride coating.
After adopting accurate single crystal technological conditions to carry out ingot casting, the polycrystal silicon ingot that forms as shown in Figure 5, wherein a figure adopts conventional spraying silicon nitride coating behind 1100 ℃ of sintering among Fig. 5, the silicon ingot picture that is used for accurate monocrystalline ingot casting, b figure is after adopting 500 ℃ of baking processing of silicon nitride coating of the present invention, the silicon ingot picture that is used for accurate monocrystalline ingot casting, as can be seen from Figure 5, significantly sticking crucible appears in the silicon liquid level place among a figure, cause silicon ingot to occur to cracking, this illustrates that conventional spraying silicon nitride coating can't satisfy the comparatively harsh accurate monocrystalline ingot casting needs of long crystal bar spare; Silicon ingot is without any sticking crucible zone among the b figure, and silicon ingot separates thoroughly with crucible.This point proof is the more conventional spraying silicon nitride coating of silicon nitride coating of the present invention in the accurate monocrystalline ingot casting demoulding of condition harshness is used, and demolding performace is more reliable.
Embodiment 3
The making method of the crystalline silicon crucible for casting ingots silicon nitride coating that the present embodiment provides, preparation flow be as shown in Figure 2:
At first, the preparation Silicon Nitride, wherein Silicon Nitride by alpha-silicon nitride powders, pure water and binding agent by weight than being that 100:150:15 is formulated.Wherein binding agent is adopted as methyl methacrylate, vinylformic acid, polyvinyl alcohol, colloid silica, its mass ratio is 1:0.1:10:10, and adopt above-mentioned Silicon Nitride to brush the easily sticking crucible zone of silicon nitride, mainly refer to the silicon liquidus zone of crucible, if adopt square crucible, also brush Silicon Nitride at rib, the angular zone of crucible inside.
Then, the silicon nitride coating that the easily sticking crucible zone of crucible is made carries out densification and non-infiltration processing, and crucible is generally fused silica crucible.Densification is: in the drying process of the easily Silicon Nitride in sticking crucible zone of crucible, by the mechanical effects such as stirring, vibration or extruding make crucible easily the silicon nitride particle in sticking crucible zone be densification and arrange, obtain the densification silicon nitride coating; It is that the equipment of ZL 201120254516.0 carries out that the mechanical effects such as stirring, vibrations and extruding can adopt the patent No., also can adopt miscellaneous equipment to carry out.Non-infiltration is treated to surface finish, polishing and the processing of adsorption dry alpha-silicon nitride powders is carried out in the silicon nitride coating surface of densification, obtains the non-infiltration silicon nitride coating.
Then, other zone preparation silicon nitride coating at the crucible inwall because other zone of crucible inwall is relatively low to density and the requirement of strength of silicon nitride coating, can adopt the mode of cast or cast+roller coat to prepare.
At last, above-mentioned silicon nitride coating is carried out 500 ℃ of baking processing, namely make obtaining crystalline silicon crucible for casting ingots silicon nitride coating.
After adopting efficient polycrystalline processing condition to carry out ingot casting, the efficient polycrystal silicon ingot of formation.As shown in Figure 6, wherein a figure adopts conventional spraying silicon nitride coating behind 1100 ℃ of sintering among Fig. 6, the picture that is used for the efficient polysilicon of ingot casting, b figure is after adopting 500 ℃ of baking processing of silicon nitride coating of the present invention, the picture that is used for efficient polycrystalline, as can be seen from Figure 6, local sticking crucible appears in the silicon liquid level place among a figure, illustrates to adopt conventional spray-on coating to bring sticking crucible hidden danger to efficient polycrystalline; Silicon ingot is without any sticking crucible zone among the b figure, and silicon ingot separates thoroughly with crucible.This point proof is the more conventional spraying silicon nitride coating of silicon nitride coating of the present invention in the efficient polycrystalline cast ingot demoulding is used, and demolding performace is more reliable.
Embodiment 4
The making method of the crystalline silicon crucible for casting ingots silicon nitride coating that the present embodiment provides, preparation flow be as shown in Figure 2:
At first, the preparation Silicon Nitride, wherein Silicon Nitride by alpha-silicon nitride powders, pure water and binding agent by weight than being that 100:450:0.1 is formulated.Wherein binding agent is adopted as in methyl methacrylate, vinylformic acid, polyvinyl alcohol or the colloid silica any and all can, adopt vinylformic acid in the present embodiment, and adopt above-mentioned Silicon Nitride to brush the easily sticking crucible zone of silicon nitride, mainly refer to the silicon liquidus zone of crucible.
Then, the silicon nitride coating that the easily sticking crucible zone of crucible is made carries out densification and non-infiltration processing, and crucible is generally fused silica crucible.Densification is: in the drying process of the easily Silicon Nitride in sticking crucible zone of crucible, by the mechanical effects such as stirring, vibration or extruding make crucible easily the silicon nitride particle in sticking crucible zone be densification and arrange, obtain the densification silicon nitride coating; It is that the equipment of ZL 201120254516.0 carries out that the mechanical effects such as stirring, vibrations and extruding can adopt the patent No., also can adopt miscellaneous equipment to carry out.Non-infiltration is treated to surface finish, polishing and the processing of adsorption dry alpha-silicon nitride powders is carried out in the silicon nitride coating surface of densification, obtains the non-infiltration silicon nitride coating.
Then, other zone preparation silicon nitride coating at the crucible inwall because other zone of crucible inwall is relatively low to density and the requirement of strength of silicon nitride coating, can adopt the mode of cast to prepare.
At last, above-mentioned silicon nitride coating is carried out 300 ℃ of baking processing, namely make obtaining crystalline silicon crucible for casting ingots silicon nitride coating.
The present invention will be described more than to enumerate specific embodiment.It is pointed out that above embodiment only for the invention will be further described, does not represent protection scope of the present invention, nonessential modification and adjustment that other people prompting according to the present invention is made still belong to protection scope of the present invention.
Claims (8)
1. the making method of a crystalline silicon crucible for casting ingots silicon nitride coating, it is characterized in that: adopt the method for liquid deposition after the easily sticking crucible zone of crucible inwall makes silicon nitride coating, this zone silicon nitride coating is carried out densification and non-infiltration processing, and adopt the method for liquid deposition to make silicon nitride coating in other zone of crucible inwall, at last silicon nitride coating is carried out low-temperature bake or non-sintered processing, obtain crystalline silicon crucible for casting ingots silicon nitride coating.
2. the making method of crystalline silicon crucible for casting ingots silicon nitride coating according to claim 1 is characterized in that: the easily sticking crucible zone of described crucible inwall is mainly rib, the angular zone of silicon liquidus zone and the crucible inside of crucible.
3. the making method of crystalline silicon crucible for casting ingots silicon nitride coating according to claim 1 and 2, it is characterized in that: the mode that makes silicon nitride coating is: directly Silicon Nitride is coated on the easily sticking crucible zone of crucible inwall or other zone of crucible inwall, silicon nitride particle autodeposition in the Silicon Nitride is coated Silicon Nitride on the inwall of crucible.
4. the making method of crystalline silicon crucible for casting ingots silicon nitride coating according to claim 3 is characterized in that: described Silicon Nitride by alpha-silicon nitride powders, pure water and binding agent by weight than for 100:70 ~ 450:0.1 ~ 15 formulated.
5. the making method of crystalline silicon crucible for casting ingots silicon nitride coating according to claim 4, it is characterized in that: described binding agent is one or more in methyl methacrylate, vinylformic acid, polyvinyl alcohol and the colloid silica.
6. the making method of crystalline silicon crucible for casting ingots silicon nitride coating according to claim 1 and 2, it is characterized in that: described densification is: in the drying process of the easily Silicon Nitride in sticking crucible zone of crucible, the silicon nitride particle that makes crucible easily glue the crucible zone by stirring, vibration or extrusion machinery effect is the densification arrangement, obtains the densification silicon nitride coating.
7. the making method of crystalline silicon crucible for casting ingots silicon nitride coating according to claim 1 and 2, it is characterized in that: described non-infiltration is treated to surface finish, polishing and adsorption dry silicon nitride powder is carried out in the silicon nitride coating surface of densification, obtains the non-infiltration silicon nitride coating.
8. the making method of crystalline silicon crucible for casting ingots silicon nitride coating according to claim 1 and 2 is characterized in that: the temperature when low-temperature bake is processed is for being lower than 500 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210369325.8A CN102898034B (en) | 2012-09-28 | 2012-09-28 | Method for manufacturing silicon nitride coating of crucible for crystalline silicon ingot casting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210369325.8A CN102898034B (en) | 2012-09-28 | 2012-09-28 | Method for manufacturing silicon nitride coating of crucible for crystalline silicon ingot casting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102898034A true CN102898034A (en) | 2013-01-30 |
| CN102898034B CN102898034B (en) | 2015-02-18 |
Family
ID=47570562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210369325.8A Active CN102898034B (en) | 2012-09-28 | 2012-09-28 | Method for manufacturing silicon nitride coating of crucible for crystalline silicon ingot casting |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102898034B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288357A (en) * | 2013-06-20 | 2013-09-11 | 天津英利新能源有限公司 | Silicon nitride solution and preparation method, and polysilicon ingot casting crucible and making method thereof |
| CN107417301A (en) * | 2017-08-18 | 2017-12-01 | 晶科能源有限公司 | A kind of silicon nitride coating preparation method of quartz crucible for casting polycrystalline silicon ingot |
| CN107747124A (en) * | 2017-11-07 | 2018-03-02 | 晶科能源有限公司 | A kind of anti-sticking crucible method of polycrystalline cast ingot |
| CN112536200A (en) * | 2019-09-21 | 2021-03-23 | 中材江苏太阳能新材料有限公司 | Side wall improved coating crucible for ingot single polycrystal and preparation method thereof |
| CN115261798A (en) * | 2021-04-30 | 2022-11-01 | 云谷（固安）科技有限公司 | Crucible and evaporation device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6296349A (en) * | 1985-10-22 | 1987-05-02 | Toshiba Ceramics Co Ltd | Quartz glass reaction tube for heat-treatment of semiconductor |
| EP0288051A1 (en) * | 1987-04-24 | 1988-10-26 | Tosoh Corporation | High-hardness silica glass and method of producing same |
| JPH01305835A (en) * | 1988-05-31 | 1989-12-11 | Nippon Tungsten Co Ltd | Silicon nitride coated quartz glass vessel |
| US20060137397A1 (en) * | 2004-12-29 | 2006-06-29 | Bookbinder Dana C | High transmission synthetic silica glass and method of making same |
| CN1849269A (en) * | 2003-09-11 | 2006-10-18 | 瓦克化学股份公司 | Method for producing an Si3N4 coated SiO2 molded body |
| CN102417308A (en) * | 2011-09-03 | 2012-04-18 | 江西旭阳雷迪高科技股份有限公司 | Ingot casting quartz crucible silicon nitride coating sintering-free technology |
-
2012
- 2012-09-28 CN CN201210369325.8A patent/CN102898034B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6296349A (en) * | 1985-10-22 | 1987-05-02 | Toshiba Ceramics Co Ltd | Quartz glass reaction tube for heat-treatment of semiconductor |
| EP0288051A1 (en) * | 1987-04-24 | 1988-10-26 | Tosoh Corporation | High-hardness silica glass and method of producing same |
| JPH01305835A (en) * | 1988-05-31 | 1989-12-11 | Nippon Tungsten Co Ltd | Silicon nitride coated quartz glass vessel |
| CN1849269A (en) * | 2003-09-11 | 2006-10-18 | 瓦克化学股份公司 | Method for producing an Si3N4 coated SiO2 molded body |
| US20060137397A1 (en) * | 2004-12-29 | 2006-06-29 | Bookbinder Dana C | High transmission synthetic silica glass and method of making same |
| CN102417308A (en) * | 2011-09-03 | 2012-04-18 | 江西旭阳雷迪高科技股份有限公司 | Ingot casting quartz crucible silicon nitride coating sintering-free technology |
Non-Patent Citations (3)
| Title |
|---|
| MICHELLE MCCANN等: "SHORT COMMUNICATION: Surface passivation by rehydrogenation of silicon-nitride-coated silicon wafers", 《PROGRESS IN PHOTOVOLTAICS: RESEARCH AND APPLICATIONS》 * |
| 朱录涛: "太阳能多晶硅铸锭用熔融石英坩埚氮化硅涂层的制备", 《襄樊学院学报》 * |
| 袁向东等: "多晶硅铸锭涂层用高纯SI3N4微粉的研究进展与展望", 《硅酸盐通报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288357A (en) * | 2013-06-20 | 2013-09-11 | 天津英利新能源有限公司 | Silicon nitride solution and preparation method, and polysilicon ingot casting crucible and making method thereof |
| CN103288357B (en) * | 2013-06-20 | 2016-03-30 | 天津英利新能源有限公司 | Silicon nitride solution and preparation method thereof, crucible used for polycrystalline silicon ingot casting and preparation method thereof |
| CN107417301A (en) * | 2017-08-18 | 2017-12-01 | 晶科能源有限公司 | A kind of silicon nitride coating preparation method of quartz crucible for casting polycrystalline silicon ingot |
| CN107747124A (en) * | 2017-11-07 | 2018-03-02 | 晶科能源有限公司 | A kind of anti-sticking crucible method of polycrystalline cast ingot |
| CN112536200A (en) * | 2019-09-21 | 2021-03-23 | 中材江苏太阳能新材料有限公司 | Side wall improved coating crucible for ingot single polycrystal and preparation method thereof |
| CN112536200B (en) * | 2019-09-21 | 2022-04-01 | 中材江苏太阳能新材料有限公司 | Side wall improved coating crucible for ingot single polycrystal and preparation method thereof |
| CN115261798A (en) * | 2021-04-30 | 2022-11-01 | 云谷（固安）科技有限公司 | Crucible and evaporation device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102898034B (en) | 2015-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102898034B (en) | Method for manufacturing silicon nitride coating of crucible for crystalline silicon ingot casting | |
| CN103382128B (en) | Ceramic filter core containing cocoanut-shell activated carbon and preparation method thereof | |
| CN106801252B (en) | A kind of quartz ceramic crucible for polycrystalline silicon ingot casting and preparation method thereof | |
| CN102221293B (en) | Preparation method of coating for melting crucible | |
| CN101348324A (en) | Non-transparent quartz crucible for polysilicon crystallization and manufacturing method thereof | |
| CN206204475U (en) | A kind of crucible used for polycrystalline silicon ingot casting | |
| CN107619226A (en) | A kind of honeycombed cement film and its production and use | |
| CN102877126A (en) | Large polycrystalline silicon crucible, coating slurry thereof and preparation method of coating | |
| CN103014852A (en) | Casting method of efficient polycrystalline silicon ingot | |
| CN103553624B (en) | Silicon carbide ceramics rotor material prepared by a kind of gel casting forming and method thereof | |
| JP2001198648A (en) | Casting mold for casting silicon ingot and method for manufacturing the same | |
| CN113443903B (en) | Preparation method of oversized cuboid fused quartz crucible and method for producing hollow square silicon core by using crucible | |
| CN102167626A (en) | Preparation method of ceramic crucible coating layer for ingoting polysilicon | |
| CN105000890A (en) | Preparation method of large-size silicon nitride crucible | |
| CN103382572A (en) | Crucible for enabling polycrystalline silicon ingot to be free of black edge and preparation method thereof | |
| CN102367572B (en) | Sintering-free spraying method of polysilicon ingot crucible | |
| CN103305910A (en) | Crucible for silicon ingot casting and preparation method of inner side coating thereof | |
| CN105645782A (en) | Manufacturing method for efficient spraying-free fused quartz crucible for polycrystalline silicon ingot casting | |
| CN102225837B (en) | Manufacture method of spray-free fused quartz crucible used for polycrystalline silicon cast ingots | |
| CN202717875U (en) | Crucible for silicon ingot and preparation method of coating on inner side thereof | |
| CN110803943B (en) | Low-impurity spray-free crucible for casting polycrystal and ingot single crystal and preparation method thereof | |
| CN104060324A (en) | Demolding layer applied to polycrystalline silicon ingot casting, polycrystalline silicon ingot casting method and crucible for ingot casting | |
| CN105603374A (en) | Method for preparing Si3N4 film on polycrystalline silicon ingot cast crucible | |
| CN203393255U (en) | Crucible for realizing no black edges of polycrystalline silicon cast ingot | |
| JP2013095652A (en) | Silica sintered body crucible |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |