JPH0154317B2 - - Google Patents
Info
- Publication number
- JPH0154317B2 JPH0154317B2 JP28135584A JP28135584A JPH0154317B2 JP H0154317 B2 JPH0154317 B2 JP H0154317B2 JP 28135584 A JP28135584 A JP 28135584A JP 28135584 A JP28135584 A JP 28135584A JP H0154317 B2 JPH0154317 B2 JP H0154317B2
- Authority
- JP
- Japan
- Prior art keywords
- growing
- crystals
- water
- crystal
- kdp
- 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.)
- Expired
Links
- 239000013078 crystal Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 244000005700 microbiome Species 0.000 claims description 8
- 238000002109 crystal growth method Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical class [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
（産業上の利用分野）
本発明は高出力レーザー用非線形光学結晶の作
成方法、さらに詳しくは、KOP（リン酸第１カリ
ウム）、DKDP（重水素化リン酸第１カリウム）、
ADP（リン酸第１アンモニウム）等の水溶性の作
成方法に関するものである。
（従来の技術）
従来、水溶性結晶は蒸発法、温度降下法、濃度
―定法、電気分解法、電気透析法等の方法で育成
されている。上述した方法においては、結晶育成
に水溶性を用いるため比較的低温（約80℃以下）
のもとで結晶の育成が行われている。
（発明が解決しようとする問題点）
育成された結晶は最近特にレーザー用素子とし
て利用されることが多くなつたが、従来の方法で
育成された水溶性結晶はいずれもレーザー耐損傷
性が低く、特に高出力レーザーではその耐損傷性
に問題があつた。
これは、従来の育成法では結晶育成温度が低い
ため結晶育成期間中に水溶液内に微生物等が発生
し、これが育成中の結晶に異物として取り込まれ
るためであることが最近になつてわかつた。この
種の異物は耐レーザー損傷性が低いため、レーザ
ー光線照射時に結晶中に損傷を生じていた。
本発明の目的は上述した不具合を解消して、結
晶育成中に紫外線を水溶液に照射し、水溶液の殺
菌を計り、微生物等の発生を抑えながら結晶育成
を行うことにより、耐レーザー損傷性の高い水溶
性結晶を育成する方法を提供しようとするもので
ある。
（問題点を解決するための手段）
本発明の水溶性結晶の育成法は、水溶液から比
較的低温のもとで結晶を育成する水溶性結晶の育
成法において、紫外線を水溶液に照射し水溶液中
の微生物等の発生を防ぐことにより、耐レーザー
損傷性の高い結晶を育成することを特徴とするも
のである。
（作 用）
従来の水溶性結晶育成法では、生成して結晶に
悪影響を及ぼす上述した水溶液中の微生物発生に
関しては注意が払われていない。本発明は、結晶
育成期間中水溶液に紫外線を照射するという簡単
な方法で微生物の発生を防ぎ、その結果耐レーザ
ー損傷性の高い結晶を得ることができることを見
出したことによる。ここで、Ｘ線、ガンマ線、レ
ーザー光線等も紫外線以外に考え得るが、Ｘ線、
ガンマ線では水溶液に対する透過性がないため殺
菌の効果は少なく、装置も極めて高価となり、レ
ーザー光線を用いる場合も殺菌効果を持たせるに
は紫外域の光にする必要があり装置が極めて高価
となるため、本発明では紫外線を使用した。
なお、本発明の方法は、結晶育成方法の種類お
よび育成する結晶の種類を問わず、どの方法およ
び結晶の種類でも適用可能であり、特にそのうち
KDP、DKDP、ADP等の作成に好適である。
（実施例）
以下、本発明を図面を参照して詳細に説明す
る。
第１図は本発明の水溶性結晶の育成法を実施す
る装置の一実施例を示す線図である。第１図に示
す実施例では、水溶性結晶としてKDP結晶を、
育成法としては温度降下法を例にとり説明する。
KDP結晶を温度降下法で育成する場合には、60
℃〜30℃の温度領域で育成することが多く室温に
近いため、一般に二重構造の槽により温度制御特
性を良好に保つ必要がある。以下、結晶育成の方
法について詳述する。
まず、内槽１に超純水とKDP材料を入れる。
同時に紫外線ランプ１０を点灯し、殺菌を開始す
る。内槽１と外線２との間に水１５を満たし、こ
の水１５をヒーター３により加熱すると同時に撹
拌器４により撹拌する。水１５を加熱することに
より、内槽１内の溶液を一旦育成開始温度以上に
加熱し、KDP材料を十分に溶解してKDP溶液１
４を得る。この段階でKDP溶液１４を内槽ふた
１２中に設けたKDP溶液フイルター用孔１３を
介して図示しないフイルターに導き、フイルター
により十分ろ過した後、再び内槽１中へ戻してい
る。
次に、内槽１の種結晶取付け台６にKDP種結
晶７を配置した後、KDP溶液１４中の異物をフ
イルターによりさらに除去する。除去作業終了
後、KDP溶液フイルター用孔１３を閉じる。そ
の後溶液の温度を下げ溶液を過飽和状態にし、以
下徐々に温度を降下させていき結晶育成を行う。
温度のコントロールはヒーター３と外槽温度コン
トロール用温度センサー５により行つている。ま
た、KDP溶液１４の温度分布を一定に保つため、
KDP溶液１４を撹拌用プロペラ９により常時撹
拌している。KDP溶液１４の温度は温度モニタ
ー用センサー１１で常に監視している。
紫外線ランプ１０は育成終了まで常時点灯して
おき、KDP溶液１４内の微生物発生を防いでい
る。また、紫外線を照射しているため、内槽１、
種結晶取付け台６、溶液撹拌用プロペラ９、温度
モニター用センサー１１、内槽ふた１２等は、紫
外線劣化の生じない材料を用いる必要がある。
実施例 １
第２図に示す形状の、従来の方法により育成し
たKDP結晶と上述した本発明の方法により育成
したKDP結晶を準備した。第２図において、２
１は種結晶、２２は育成結晶である。また、その
育成条件は以下のようであり、従来法の場合は紫
外線ランプを使用しなかつた。
●使用した紫外線ランプ
出力10W、主波長2537Å
●使用した超純水 ８
●使用したKDP材料 2800ｇ（試薬特級）
●育成開始温度 44.80℃
●育成終了温度 35.35℃
●育成期間 28日間
●溶液温度降下率 0.3℃／day
●種結晶 ５cm×５cm×１cm
（Ｚカツト板）
●溶液撹拌 プロペラ法
その後、波長1.06μm、パルス幅1nsec.のレーザ
ーを使用して耐レーザー損傷テストを行つた結
果、第１表に示す結果が得られた。
(Industrial Application Field) The present invention relates to a method for producing a nonlinear optical crystal for high-power lasers, and more specifically, KOP (potassium monophosphate), DKDP (deuterated potassium monophosphate),
This paper relates to a method for producing water-soluble ADP (ammonium phosphate) and the like. (Prior Art) Water-soluble crystals have conventionally been grown by methods such as an evaporation method, a temperature drop method, a concentration method, an electrolysis method, and an electrodialysis method. In the above method, since water solubility is used for crystal growth, the temperature is relatively low (approximately 80℃ or less).
Crystals are grown under (Problems to be Solved by the Invention) Grown crystals have recently been increasingly used, especially as laser elements, but all water-soluble crystals grown by conventional methods have low laser damage resistance. However, there were problems with its damage resistance, especially with high-power lasers. It has recently been found that this is because in conventional growth methods, the crystal growth temperature is low, so microorganisms and the like are generated in the aqueous solution during the crystal growth period, and these microorganisms are incorporated into the growing crystal as foreign matter. Since this type of foreign matter has low laser damage resistance, damage was caused in the crystal during laser beam irradiation. The purpose of the present invention is to eliminate the above-mentioned problems, and to achieve high laser damage resistance by irradiating an aqueous solution with ultraviolet rays during crystal growth, sterilizing the aqueous solution, and growing the crystal while suppressing the generation of microorganisms. The present invention aims to provide a method for growing water-soluble crystals. (Means for Solving the Problems) The method for growing water-soluble crystals of the present invention is a method for growing water-soluble crystals in which crystals are grown from an aqueous solution at a relatively low temperature. This method is characterized by growing crystals with high laser damage resistance by preventing the generation of microorganisms and the like. (Function) In the conventional water-soluble crystal growth method, no attention is paid to the above-mentioned generation of microorganisms in the aqueous solution that are generated and have an adverse effect on the crystals. The present invention is based on the discovery that the generation of microorganisms can be prevented by a simple method of irradiating an aqueous solution with ultraviolet rays during the crystal growth period, and as a result, crystals with high laser damage resistance can be obtained. Here, X-rays, gamma rays, laser beams, etc. can also be considered in addition to ultraviolet rays, but
Gamma rays have little sterilizing effect because they have no permeability to aqueous solutions, and the equipment is extremely expensive. Even when using laser beams, in order to have a sterilizing effect, the light needs to be in the ultraviolet region, making the equipment extremely expensive. In the present invention, ultraviolet light was used. Note that the method of the present invention can be applied to any method and type of crystal, regardless of the type of crystal growth method and the type of crystal to be grown.
Suitable for creating KDP, DKDP, ADP, etc. (Example) Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a diagram showing one embodiment of an apparatus for carrying out the method for growing water-soluble crystals of the present invention. In the example shown in Fig. 1, KDP crystal is used as the water-soluble crystal.
The growth method will be explained using a temperature drop method as an example.
When growing KDP crystals by temperature drop method, 60
Since they are often grown in a temperature range of ℃ to 30℃, which is close to room temperature, it is generally necessary to maintain good temperature control characteristics using a double-layered tank. The crystal growth method will be described in detail below. First, put ultrapure water and KDP material into inner tank 1.
At the same time, the ultraviolet lamp 10 is turned on to start sterilization. Water 15 is filled between the inner tank 1 and the outer line 2, and the water 15 is heated by a heater 3 and stirred by a stirrer 4 at the same time. By heating the water 15, the solution in the inner tank 1 is heated to a temperature higher than the growth start temperature, and the KDP material is sufficiently dissolved to form the KDP solution 1.
Get 4. At this stage, the KDP solution 14 is guided to a filter (not shown) through the KDP solution filter hole 13 provided in the inner tank lid 12, and after being thoroughly filtered by the filter, it is returned to the inner tank 1 again. Next, after placing the KDP seed crystal 7 on the seed crystal mount 6 of the inner tank 1, foreign matter in the KDP solution 14 is further removed using a filter. After the removal work is completed, close the KDP solution filter hole 13. Thereafter, the temperature of the solution is lowered to bring the solution into a supersaturated state, and the temperature is then gradually lowered to grow crystals.
The temperature is controlled by a heater 3 and a temperature sensor 5 for controlling the temperature of the outer tank. In addition, in order to keep the temperature distribution of the KDP solution 14 constant,
The KDP solution 14 is constantly stirred by a stirring propeller 9. The temperature of the KDP solution 14 is constantly monitored by a temperature monitoring sensor 11. The ultraviolet lamp 10 is kept on at all times until the end of the growth to prevent the generation of microorganisms in the KDP solution 14. In addition, since ultraviolet rays are irradiated, the inner tank 1,
The seed crystal mounting stand 6, the solution stirring propeller 9, the temperature monitoring sensor 11, the inner tank lid 12, etc. must be made of materials that are not subject to UV deterioration. Example 1 A KDP crystal grown by a conventional method and a KDP crystal grown by the above-described method of the present invention having the shape shown in FIG. 2 were prepared. In Figure 2, 2
1 is a seed crystal, and 22 is a grown crystal. Further, the growth conditions are as follows, and in the case of the conventional method, no ultraviolet lamp was used. ●Ultraviolet lamp used Output: 10W, dominant wavelength: 2537Å ●Ultrapure water used: 8 ●KDP material used: 2800g (reagent grade) ●Growing start temperature: 44.80℃ ●Growing end temperature: 35.35℃ ●Growing period: 28 days ●Solution temperature drop rate 0.3℃/day ●Seed crystal 5cm x 5cm x 1cm (Z-cut plate) ●Solution stirring Propeller method After that, we performed a laser damage resistance test using a laser with a wavelength of 1.06μm and a pulse width of 1nsec.The results are shown in Table 1. The results shown are obtained.
【表】
第１表から明らかなように、本発明の方法によ
り作成したKDP結晶は従来の方法により作成し
たKDP結晶と比較して約３〜５倍の耐レーザー
損傷性向上が認められた。
（発明の効果）
以上詳細に説明したところから明らかなよう
に、本発明の高レーザー耐損傷性を持つ水溶液結
晶の育成法よれば、結晶育成時に紫外線を照射す
ることにより、耐レーザー損傷性の高い水溶液結
晶を得ることができ、特に高出力レーザー用素子
として有効に使用することができる。[Table] As is clear from Table 1, the KDP crystal produced by the method of the present invention was found to have about 3 to 5 times improved laser damage resistance compared to the KDP crystal produced by the conventional method. (Effects of the Invention) As is clear from the detailed explanation above, according to the method of growing an aqueous solution crystal with high laser damage resistance of the present invention, by irradiating ultraviolet rays during crystal growth, laser damage resistance can be improved. It is possible to obtain high-quality aqueous crystals, and it can be particularly effectively used as a high-power laser element.
第１図は、本発明の水溶性結晶の育成法を実施
する装置の一実施例を示す線図、第２図は、育成
した単結晶の形状を示す線図である。
１……内槽、２……外槽、３……ヒーター、４
……撹拌器、５……外槽温度コントロール用温度
センサー、６……種結晶取付台、７……種結晶、
８……KDP結晶、９……撹拌用プロペラ、１０
……紫外線ランプ、１１……温度モニター用セン
サー、１２……内槽ふた、１３……KDP溶液フ
イルター用孔、１４……KDP溶液、１５……水。
FIG. 1 is a diagram showing an example of an apparatus for implementing the water-soluble crystal growth method of the present invention, and FIG. 2 is a diagram showing the shape of a grown single crystal. 1...Inner tank, 2...Outer tank, 3...Heater, 4
... Stirrer, 5 ... Temperature sensor for outer tank temperature control, 6 ... Seed crystal mounting stand, 7 ... Seed crystal,
8... KDP crystal, 9... Stirring propeller, 10
...UV lamp, 11...Temperature monitoring sensor, 12...Inner tank lid, 13...KDP solution filter hole, 14...KDP solution, 15...Water.
Claims (1)
る水溶性結晶の育成法において、紫外線を水溶液
に照射し水溶液中の微生物等の発生を防ぐことに
より、耐レーザー損傷性の高い結晶を育成するこ
とを特徴とする水溶性結晶の育成法。 ２ 前記紫外線を、水溶性結晶の育成開始時から
育成終了時まで常時照射することを特徴とする特
許請求の範囲第１項記載の水溶性結晶の育成法。[Claims] 1. In a water-soluble crystal growth method in which crystals are grown from an aqueous solution at a relatively low temperature, laser damage resistance is achieved by irradiating the aqueous solution with ultraviolet rays to prevent the generation of microorganisms, etc. in the aqueous solution. A method for growing water-soluble crystals characterized by growing crystals with high . 2. The method for growing water-soluble crystals according to claim 1, characterized in that the ultraviolet rays are constantly irradiated from the start of growing the water-soluble crystals until the end of growing them.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28135584A JPS61155284A (en) | 1984-12-27 | 1984-12-27 | Growth of water-soluble crystal having high resistance to damage caused by laser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28135584A JPS61155284A (en) | 1984-12-27 | 1984-12-27 | Growth of water-soluble crystal having high resistance to damage caused by laser |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61155284A JPS61155284A (en) | 1986-07-14 |
| JPH0154317B2 true JPH0154317B2 (en) | 1989-11-17 |
Family
ID=17637953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28135584A Granted JPS61155284A (en) | 1984-12-27 | 1984-12-27 | Growth of water-soluble crystal having high resistance to damage caused by laser |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61155284A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01103979A (en) * | 1987-10-15 | 1989-04-21 | Univ Osaka | Method for growing water soluble optical single crystal having resistance to scratching by high-output laser |
| CN102534778A (en) * | 2012-03-14 | 2012-07-04 | 青岛大学 | Omnibearing growing method for KDP (Potassium Dihydrogen Phosphate) crystals |
| CN110359081B (en) * | 2019-08-08 | 2021-02-19 | 江南大学 | Method for controlling aspect ratio in crystal growth process |
-
1984
- 1984-12-27 JP JP28135584A patent/JPS61155284A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61155284A (en) | 1986-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3620555B1 (en) | Compound of cesium fluorooxoborate, non-linear optical crystal of cesium fluorooxoborate, preparation method therefor and use thereof | |
| CN107265473B (en) | Compound fluoboric acid rubidium and fluoboric acid rubidium nonlinear optical crystal and preparation method and purposes | |
| CN111334858B (en) | Compound barium fluoborate, barium fluoborate nonlinear optical crystal, preparation method and application | |
| CN108588833A (en) | Compound fluoboric acid calcium and fluoroboric acid calcium non-linear optical crystal and preparation method and purposes | |
| US6261420B1 (en) | Process for producing amorphous material containing single crystal or polycrystal and material produced | |
| CN106948003A (en) | Compound potassium fluoborate and potassium fluoborate nonlinear optical crystal and preparation method and purposes | |
| CN108004594A (en) | Cesium iodate nonlinear optical crystal and its preparation method and application | |
| CN114057207B (en) | Compound sodium octadecafluoride and sodium octafluoride nonlinear optical crystal, and preparation method and application thereof | |
| JPH0154317B2 (en) | ||
| US5879590A (en) | Low conductivity, doped KTIOPO4 and devices based thereon | |
| CN112501692B (en) | Compound lead barium boron oxyfluoride and lead barium boron oxyfluoride nonlinear optical crystal, preparation method and application | |
| CN109748256A (en) | The preparation method and purposes of phosphoric acid rubidium lead bismuth and its nonlinear optical crystal | |
| CN108286072A (en) | Compound one is fluorinated sodium tetraborate and a fluorination sodium tetraborate nonlinear optical crystal and preparation method and purposes | |
| Joshi et al. | Single crystal growth of ferroelectric potassium dihydrogen orthophosphate in silica gels | |
| Shou-Quan et al. | Hydrothermal growht of KTP crystals in the medium range of temperature and pressure | |
| CN1421551A (en) | Combined crucible rotating and molten salt pulling method for growing RE3+: KGd (WO4)2 laser crystal | |
| JPH01103979A (en) | Method for growing water soluble optical single crystal having resistance to scratching by high-output laser | |
| US5322588A (en) | Method for producing KTIOPO4 single crystal | |
| Manivannan et al. | Investigation on Nucleation Kinetics, Growth and Nonlinear Optical Properties of L-Cystine Hydrochloride Crystal | |
| DE3419722C2 (en) | ||
| JPH04270195A (en) | Production of nonlinear optical single crystal | |
| CN113913936B (en) | Compound lanthanum boron oxyfluoride and lanthanum boron oxyfluoride nonlinear optical crystal, and preparation method and application thereof | |
| CN114959915B (en) | Device for improving growth speed and utilization rate of KDP crystal and growth method thereof | |
| US3418086A (en) | Lithium meta-niobate crystalline growth from melt containing magnesium oxide | |
| CN116427031A (en) | Compound sodium fluoroborate and sodium fluoroborate nonlinear optical crystal, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |