Method for producing organic crystal and crystal growth cell therefor

• US 5,363,797 A
• Filed: 05/04/1992
• Issued: 11/15/1994
• Est. Priority Date: 11/05/1988
• Status: Expired due to Fees

• Current Assignee: Sumitomo Electric Industries Limited (Sumitomo Corporation)
• Original Assignee: Sumitomo Electric Industries Limited (Sumitomo Corporation)
• Inventors: Oogaki, Yasuji, Hattori, Yasuhiro, Mizoguchi, Akira, Umegaki, Shinsuke, Shimizu, Yo, Uemiya, Takafumi, Uenishi, Naota
• Primary Examiner(s): KUNEMUND, ROBERT M
• Application Number:
  US07/879,105
• Time in Patent Office: 925 Days
• Field of Search: 156/600, 156/608, 156/616.3, 156/616.4, 156/616.41, 156/621, 156/624, 156/DIG. 113, 422/248
• US Class Current: 117/68
• CPC Class Codes: C30B 11/00 Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method C30B13/00, C30B15/00, C30B17/00, C30B19/00 take precedence; under a protective fluid C30B27/00
• CPC Class Codes: C30B 11/002 Crucibles or containers for supporting the melt
• CPC Class Codes: C30B 11/003 Heating or cooling of the melt or the crystallised material
• CPC Class Codes: C30B 29/54 Organic compounds
• CPC Class Codes: C30B 29/60 characterised by shape

Abstract

A method for producing an organic crystal is disclosed. One embodiment comprises maintaining a capillary tube containing a fused liquid of an organic crystal material and having a fused liquid reservoir at one end thereof at a temperature not less than the fusion point of the organic crystal material together with the fused liquid reservoir, reducing the temperature of the fused liquid in the fused liquid reservoir to precipitate seed crystals, and then slowly cooling the capillary tube successively from the end toward the other end to allow a single crystal to grow from the seed crystal in the capillary tube. Because of the large quantity of the fused liquid, a seed crystal can be formed and allowed to grow even from a fused liquid of an organic crystal material which hardly crystallizes in the form of a fused liquid. Another embodiment comprises charging a solution of an organic crystal material in a capillary tube under heat, rapidly reducing the temperature of one end of the capillary tube to precipitate polycrystals, and then slowly cooling the capillary tube successively from the end toward the other end to allow a single crystal to grow from the polycrystal as a seed crystal. A seed crystal grows from a solution of an organic crystal material under control of crystal form to obtain a single crystal which has no inversion symmetry center, is free from lattice defect or rearrangement, and less causative of a laser beam loss.

Claims

1. A method for producing an organic crystal which comprises maintain a capillary tube having an inner wall with one side and a side on the opposite side of said one side and having an inner diameter of 1 to 5 μ

m containing a fused liquid of an organic crystal material and having a fused liquid reservoir at one end thereof at a temperature not less than the fusion point of said organic crystal material together with the fused liquid reservoir, reducing the temperature of the fused liquid in said fused liquid reservoir to precipitate seed crystals, and then slowly cooling the capillary tube successively from said end toward the other end to allow a single crystal to grow from the seed crystal in the capillary tube, wherein during said slowly cooling a temperature gradient is provided from the inner wall of the capillary tube on said one side toward the inner wall of the capillary tube on said opposite side of said one side to thereby allow the single crystal to grow.

2. A method for producing an organic crystal which comprises maintaining a capillary tube having an inner wall with one side and a side on the opposite side of said one side and having an inner diameter of 1 to 5 μ

m containing a fused liquid of an organic crystal material and having a fused liquid reservoir at one end thereof at a temperature not less than the fusion point of said organic crystal material together with the fused liquid reservoir, reducing the temperature of the fused liquid in said fused liquid reservoir while said fused liquid is in contact with a seed crystal which is provided outside the heating zone to thereby allow the seed crystal to grow, and then slowly cooling the capillary tube successively from said end toward the other end to allow a single crystal to grow from the seed crystal in the capillary tube, wherein during said slowly cooling a temperature gradient is provided from the inner wall of the capillary tube on said one side toward the inner wall of the capillary tube on said opposite side of said one side to thereby allow the single crystal to grow.

3. A method for producing an organic crystal which comprises charging a solution of an organic crystal material in a capillary tube under heat, said capillary tube having an inner wall with one side and a side on the opposite side of said one side, rapidly reducing the temperature of one end of the capillary tube to precipitate polycrystals, and then slowly cooling the capillary tube successively from said end toward the other end to allow a single crystal to grow from the polycrystal as a seed crystal.

4. A method as claimed in claim 3, wherein a liquid reservoir containing said solution of an organic crystal material is provided at one end of said capillary tube.

5. A method as claimed in claim 4, wherein said liquid reservoir, which constitute on organic crystal growth cell with said capillary tube, is sealed;

said solution of an organic crystal material is heated to a temperature not lower than the boiling point of a solvent contained in said solution so as to completely dissolve said organic crystal material in said solution; and

one end of said capillary tube is opend so that said solution is drained from said capillary tube, and simultaneously the temperature of said end of the capillary tube is rapidly reduced or the solvent of the solution at said end of the capillary tube is evaporated, so as to attach said seed crystal at said end of the capillary tube.

16. The method of claim 3 wherein said capillary tube has an inner diameter of 5 μ

m or less.

6. A method for producing an organic crystal which comprises slowly cooling a capillary tube containing a solution of an organic crystal material under heat, said capillary tube having an inner wall with one side and a side on the opposite side of said one side, and said capillary tube being fitted with a seed crystal at one end thereof so that said solution is in contact with said seed crystal successively from said end toward the other end to allow a single crystal to grow from said seed crystal in the capillary tube.

7. A method as claimed in claim 6, wherein a liquid reservoir containing said solution of an organic crystal material is provided at one end of said capillary tube.

8. A method as claimed in claim 7, wherein said liquid reservoir, which constitute on organic crystal growth cell with said capillary tube, is sealed;

said solution of an organic crystal material is heated to a temperature not lower than the boiling point of a solvent contained in said solution so as to completely dissolve said organic crystal material in said solution; and

one end of said capillary tube is opend so that said solution is drained from said capillary tube, and simultaneously the temperature of said end of the capillary tube is rapidly reduced or the solvent of the solution at said end of the capillary tube is evaporated, so as to attach said seed crystal at said end of the capillary tube.

17. The method of claim 8 wherein said capillary tube has an inner diameter of 5 μ

m or less.

9. A method for producing an organic crystal while controlling the crystal direction of the organic crystal which comprises slowly cooling a capillary tube which has a circular cross-section and which contains a fused liquid or solution of an organic crystal material under heat, successively from one end thereof toward the other end with a temperature gradient provided from the inner wall of the capillary tube on one side toward the inner wall on the opposite side to thereby allow a single crystal to grow.

10. A method as claimed in claim 9, wherein a heater is provided on only one side of said capillary tube.

11. A method as claimed in claim 10, wherein said capillary tube containing a fused liquid or solution of an organic crystal material is placed holizontally in a heating furnace comprising a heater at the bottom thereof, an open top, a high-temperature part kept at a temperature higher than the fusion point of said organic crystal material, and a low-temperature part kept at a temperature lower than the fusion point of said organic crystal material;

and said capillary tube is moved holizontally from said high-temperature part to said low-temperature part.

12. A method for producing an organic crystal while controlling the crystal direction of the organic crystal which comprises cooling a capillary tube which has a circular cross-section and which contains a fused liquid or solution of an organic crystal material under heat, the inner wall of said capillary tube being modified with a coupling agent, successively from one thereof toward the other end to allow a single crystal to grow.

13. A method as claimed in claim 12, wherein said coupling agent is a silane coupling agent.

14. A method as claimed in claim 13, wherein said coupling agent is a monochlorosilane compound.

15. A method as claimed in claim 14, wherein said coupling agent is dimethylphenylmonochlorosilane.

18. A method for producing an organic crystal which comprises maintain a capillary tube having an inner diameter of 5 μ

m or less containing a fused liquid of an organic crystal material and having a fused liquid reservoir at one end thereof at a temperature not less than the fusion point of said organic crystal material together with the fused liquid reservoir, reducing the temperature of the fused liquid in said fused liquid reservoir to precipitate seed crystals, and then slowly cooling the capillary tube successively from said end toward the other end to allow a single crystal to grow from the seed crystal in the capillary tube, wherein the inner wall of said capillary tube is modified with a coupling agent.

19. A method for producing an organic crystal which comprises maintaining a capillary tube having an inner diameter of 5 μ

m or less containing a fused liquid of an organic crystal material and having a fused liquid reservoir at one end thereof at a temperature not less than the fusion point of said organic crystal material together with the fused liquid reservoir, reducing the temperature of the fused liquid in said fused liquid reservoir while said fused liquid is in contact with a seed crystal which is provided outside the heating zone to thereby allow the seed crystal to grow, and then slowly cooling the capillary tube successively from said end toward the other end to allow a single crystal to grow from the seed crystal in the capillary tube, wherein the inner wall of said capillary tube is modified with a coupling agent.

20. A method for producing an organic crystal which comprises charging a solution of an organic crystal material in a capillary tube under heat, rapidly reducing the temperature of one end of the capillary tube or evaporating the solvent in said solution so as to precipitate polycrystals, and then slowly cooling the capillary tube successively from said end toward the other end to allow a single crystal to grow from the polycrystal as a seed crystal, wherein the inner wall of said capillary tube is modified with a coupling agent.

21. A method for producing an organic crystal which comprises slowly cooling a capillary tube containing a solution of an organic crystal material under heat, said capillary tube being fitted with a seed crystal at one end thereof so that said solution is in contact with said seed crystal successively from said end toward the other end to allow a single crystal to grow from said seed crystal in the capillary tube, wherein the inner wall of said capillary tube is modified with a coupling agent.