캬웕톶 뗚第?36?卷뻭第뗚6?期웚?人죋?工릤?晶뺧?体쳥?学톧?报놨??Vo??ꎮ?????ꎮ??l. 36 2??∞??7年쓪?1?2月퓂????????????????????????????ꆾ??????????ꎮ?????JOURNAL OF SYNTHETIC CRYSTALS December，2∞7 二뛾价볛阳퇴离샫子ퟓ掺담入죫?KD?P?晶뺧쳥体能쓜力솦的뗄研퇐究뺿?헅张文컄彬뇲?1튻，2ꎬ郑횣国맺宗ퟚ?1，튻2ꎬ쯕苏룹根늩博?ꎬ庄欣타타欣?李ꎬ샮征헷东뚫?l?(?1ꎮ훐.맺中뿆国科톧学풺院뢣福붨建컯物훊质뷡结릹构研퇐究뺿所쯹，ꎬ뢣福州훝?3S??∞??02?;ꎻ2?.ꎮ中훐国맺科뿆学톧院풺研퇐究뺿生짺院풺，ꎬ北놱京뺩l?∞???03??9)?햪摘要튪:ꎺ놾本컄文횼旨퓚在톰寻헒找펰影쿬响퓓杂훊质퇴阳샫离ퟓ子뷸进入죫?KD?P?晶뺧体쳥能쓜力솦的뗄因틲素쯘，ꎬ컒我쏇们쪹使폃用럖分컶析뒿纯的뗄K??H?问???뫍和超뎬纯뒿水쮮(?뗧电阻ퟨ率싊;ꇝ;:.24?1??8ꎮ.?2?M?il ꆤ. c??m)?为캪原풭料쇏，ꎬ럖分뇰别볓加죫入?Ba?C?l??.ꆤ 2?H??0?,ꎬ ?Cu?C?l??.ꆤ 2?H???0和뫍?M?g?CI?2.ꆤ?6?H2?0?，ꎬ춨通맽过붵降컂温랽方쪽式뿬快쯙速짺生长뎤出돶K?D?P?晶뺧体쳥。ꆣ结2뷡?2 2 2 맻뇭쏷ꎬ??ꆰ벰??2?퓚뺧쳥훐뗄몬솿믹놾놣돖늻뇤ꎬ늻쯦웤퓚짺뎤죜튺훐솿뗄퓶듳뛸퓶듳ꎬ??2果表明，CJ+及Mg+在晶体中的含量基本保持不变，不随其在生长溶液中量的增大而增大，Cuꆰ+在퓚晶뺧体쳥中훐的뗄含몬量솿大듳?폚???2于Mg+在퓚晶뺧体쳥中훐的뗄含몬量솿;ꎻ늻不춬同的뗄쫇是ꎬ，B?i?ꆰ+퓚在晶뺧쳥体中훐的뗄含몬솿量쯦随ퟅ着웤其퓚在짺生뎤长죜溶튺液훐中솿量퓶增듳大뛸而增퓶大듳。ꆣ从듓实쪵验퇩结뷡果맻我컒们쏇推췆断뛏?出돶샫离子ퟓ냫半뺶径뫍和샫离子ퟓ쮮水뫏合죈热쫇是펰影响쿬뛾二볛价퓓杂质훊阳퇴샫离ퟓ子在퓚水쮮溶죜液튺晶뺧体쳥生짺长뎤过맽돌程中훐进뷸入죫?KD?P?晶뺧体쳥能쓜力솦的뗄重훘要튪因틲素쯘。ꆣ?关맘键볼词듊ꎺ:?K?DP?晶뺧体쳥;ꎻ뛾二볛价퇴阳离샫子ퟓ:ꎻ샫离ퟓ子냫半径뺶:ꎻ쮮水뫏合热죈?中훐춼图分럖类샠号뫅ꎺ:?07?8?1??文컄献쿗标뇪识쪶码싫ꎺ:?A?文컄章헂编뇠号뫅:ꎺI?C?削??-?9?8?5?X(??2∞??7?)?侃??-??1?2?3?0?-û5???????????????????????????????????????????????Iovestigatioo 00 the Dopiog Capability of the ?D?i?v?a?l?e?o?t? C??at?i?o??n?s? 0??0? ????????????????the KDP Crystal ?????????ꎮ???1ꆣꆯ?2 ?????????ꆪ????1ꆣꆯ?2 ??????ꆪ??1ꆣ ??????????ꆪ??ꆣ1 ZHANG Wen-bin ,ZHENG Gω_zong•,SU Gen-bo,ZHUANG Xin-xinꎬ????????ꎮ????ꆣ?ꎬꎬꎬ,LI Zheng-dongl (?1?.ꎮ ?Fu??ji?an? ?I?n?s?ti?tu??te ?o??f ?R?es?ea?r?c?h? ?o?n? ?t?he? ??S?tru?c?t?ur?e ?o??f ?M?a?tte?r?,ꎬ C??h?ine?s?e? A?c?a??de?m?y? ?o?f? S??c?ien?c?e?s?,ꎬ F?u?z?h?o?u? ??3S?∞???02?，ꎬ ?C?h?in?a;ꎻ ??2.ꎮ G??ra?du?a??te ?Sch??oo?l? ?of? t?he? ??C?hi?ne?s?e ??A?ca?d?e?m?y? ?o??f ?th?e?? ?S?ci?en?c?e?s?,ꎬ B??凹?lj?in?g?1?∞???03?9?，ꎮ ?C?h?in?a)? ??(?R配??e?i?v?e?d1??2 M?a?r?ch? ?2?∞???7)? A??b?s?t?ra?c??t:ꎺ T?h?e? ??ai?m?? ?o?f? ???????????????????????????????????????????????????????????????????????????????this paper is to investigate the factors affecting the ability of cations as impurity to ?in?c?o?rp?o?ra??te? ?th?e ?K?D??P? cr?ys?t?al.ꎮ K?H??P? ??p?o??w?d?e?r ?(A??R)? a??n?d? d?e?i?o?n?ed?? ?w?a?ter? ?(r?es?i?st?iv?i?ty? ꇝ~ ?1?8.ꎮ 2??M?f?lꆣ’?c?m?) w??er?e? 24 ?u?s?ed?? a?s? ????????????ꎬ?????ꆤ????ꎬ?????ꆤ??????????????ꆤ???????????????????????????ꎮ???????????raw materials, ß, ß and ß were doped respectively. The results 2 22 22 2????????????????????????2 ???????2 ???????????????????????????????????????????????????????ꆪ?????show that the content of Cu+ and Mg+ in the crystal basically keep constant and doesn 1 increase ~ with ??????????????????????????????????ꎬ?????????????????????2 ??????????????????????????????????????2 the increasing of that in the solution, and the content of Cu+ in the CIγstal is larger than that of Mg+ i?n?? ?????????ꎮ???????ꎮ??????????????????2 ???????????????????????????????????????????????????2???the crystal. However, the content of Ba+ in the CIγstal increases with the increasing content of Ba+ in ???????????ꎮ?????????????????????????????????????????????????????????????????????????????the solution. It can be deduced from the experimental results that both the ionic radius and the ?d?eh?y?d?r?a?t?i?o?n? h?e?a?t? a??r?e? ?t?he?? i?m?p?o?r?ta??n?t f?a?c?t?or?s ?a?f?f?e?c?t?in?g?? t?h?e?? a?b?i?li?t?y?? o??f? ?t?he?? d?i?v??al?e??n?t? c??at?i?o?n?s? t?o? i?nc?o?r??p?o?r?at?e?? t?h?e?? K??D?P ???????????????????????????????????????????ꎮ?in the process of crystal growth from solution. K?e?y?? w??o?r?d?s:ꎺ K?D??P? c??ry?s?t?al;ꎻ ?di?va??l?en?t? ?ca?t?i?o?n;ꎻ ?i?o?ni?c? r??a?d?i?u?s;ꎻ d?e?h?y?d?r?a?t?i?o?n?? ?h?ea?t? ?틽?퇔.J›1引口?K?D?P?쫇是一튻种훖长뎤期웚以틔来살被놻广맣泛랺研퇐究뺿的뗄重훘要튪晶뺧体쳥，ꎬ9?0?年쓪代듺以틔来살，ꎬ평由폚于웤其틗易폚于짺生뎤长돉成듳大뺧晶쳥体뫍和폅优良솼的뗄光맢学톧效킧?收쫕稿룥日죕期웚:ꎺ?2?∞?7?'?()?3ꆪ-?1?2?基믹金뷰项쿮目쒿:ꎺ맺国家볒8?6?3?基믹金뷰子ퟓ项쿮目쒿(?N?o?.ꎮ 8??63?-?80?4?-?2)? ?作ퟷ者헟简볲介뷩:ꎺ헅张文컄彬뇲(?1?9?8?2?-튻)?ꎬ，쓐男ꎬ，붭江컷西쪡省人죋，ꎬ硕쮶士쪿。ꆣE?-ꆪm?a?i?l:ꎺ?z?h?a?n?g?w?b?l9?8?2?@? ?fj?ir?s?m.ꎮ配??.ꎮc?n? ?通춨讯톶作ퟷ者헟:ꎺ李샮征헷东뚫，ꎬ?Eꆪ-m??ai?l:ꎺ l?z?d?@?fj?ir?s?mꎮ.?a?cꎮ.c?n??
캬웕톶 第뗚6?期웚?张헅文컄彬뇲等뗈:ꎺ뛾二볛价阳퇴샫离ퟓ子掺담入죫K?D?P?晶뺧体쳥能쓜力솦的뗄研퇐究뺿?1?2?3?1? 应펦，ꎬ뛸而ퟷ作캪为튻一훖种훘重튪要뗄的맢光톧学웷器볾件펦应폃用于폚国맺家볒点뗣火믰计볆划뮮[ꆧIJ?。ꆣ?目쒿잰前뛔对这헢方랽面쏦的뗄研퇐究뺿工릤作ퟷ主훷要튪集벯中훐在퓚以틔下쿂两솽个룶方랽面쏦:ꎺ(??1?룄)뷸改짨进设놸备뫍和짺生뎤长맽过돌程훐中뗄的릤工틕艺，ꎬ틔以뇣便쓜能릻够快뿬速쯙?生짺长뎤大듳尺돟寸듧的뗄透춸明쏷单떥晶뺧?[]ꎻ;?(?2)?研퇐究뺿K?D?P?晶뺧体쳥的뗄质훊量솿，ꎬ쳘特뇰别쫇是쾣希췻望헒找到떽影펰响쿬激벤光맢损쯰伤짋阔值횵的뗄因틲素쯘，ꎬ拟쓢通춨过맽?对뛔生짺长뎤参닎数쫽的뗄调뗷整헻及벰采닉用폃某쒳些킩晶뺧体쳥后뫳处뒦理샭技벼术쫵来살提쳡高룟晶뺧体쳥的뗄质훊量솿?[4.?5]?。ꆣ?튻一般냣죏认캪为，ꎬ뫛痕솿量뗄的퇴阳샫离ퟓ子뚼都믡会뛔对뺧晶쳥体짺生뎤长맽过돌程뫍和뺧晶体쳥质훊量솿产닺生짺较뷏大듳影펰响쿬，，ꎬ特쳘特别뇰别是쫇是三三죽价价볛阳阳퇴离离샫子子ퟓ阳?[6，~ꆣꎬ'如죧如???3ꆧ 3 Fe+ ,ꎬC?r?ꆧ+뫍和A?e?ꆧ+ꎬ洛죜液튺中훐三죽价볛阳퇴离샫子ퟓ的뗄存듦在퓚会믡明쏷显쿔抑틖制훆晶뺧面쏦，特ꎬ쳘别뇰是쫇柱훹面쏦的뗄生짺长뎤;ꎻ另쇭一튻方랽面쏦，ꎬ晶뺧体쳥中훐F?e?离샫子ퟓ?含몬量솿的뗄퓶增大듳明쏷쿔显뗘地떼导훂致뺧晶쳥体퓚在ퟏ紫췢外波늨뛎段춸透过맽率싊的뗄降붵低뗍?[7J?。ꆣ然좻而뛸应펦当떱指횸出돶的뗄是쫇，ꎬ늢并늻不쫇是쯹所폐有的뗄阳퇴离샫子ퟓ都뚼对뛔?K?D?P?晶뺧쳥体有폐显쿔著훸影펰响쿬，ꎬ폐有킩些퇴阳샫离ퟓ子닺产짺生뗄的펰影쿬响쫇是캢微죵弱뗄的ꆣ。탭许뛠多샭理싛论짏上的뗄릤工ퟷ作벯集中훐폚于寻톰找헒影펰响쿬水쮮溶죜液튺中훐的뗄金뷰?属쫴离샫子ퟓ进뷸入죫晶뺧体쳥能쓜力솦的뗄因틲素쯘?[]ꎬ从듓中훐可뿉以틔看뾴出돶，ꎬ샫离ퟓ子냫半뺶径，ꎬ샫离ퟓ子뗧电뫉荷뫍和샫离ퟓ子폫与쮮水뗄的뷡结뫏合쓜能솦力뗈等等뗈쫇是决뻶定뚨这헢?种훖能쓜力솦的뗄主훷要튪因틲素쯘，ꎬ然좻而뛸，ꎬ맘关폚于헢这랽方面쏦的뗄实쪵验퇩工릤作ퟷ并늢不늻多뛠见볻。ꆣ?以틔잰前的뗄关맘于폚K?D?P?晶뺧쳥体生짺长뎤过맽程돌中훐金뷰属쫴杂퓓质훊阳퇴离샫子ퟓ的뗄影펰响쿬大듳部늿分럖集벯中훐在퓚三죽价볛阳퇴离샫子ퟓ，ꎬ뛔对튻一볛价和뫍二뛾价볛关맘注힢?甚짵少짙。ꆣ本놾文컄希쾣望췻通춨过맽分럖析컶不늻同춬二뛾价볛阳퇴离샫子ퟓ在퓚K?D?P?晶뺧쳥体中훐含몬量솿分럖布늼的뗄不늻同춬，ꎬ쓜能릻够뗃得돶出펰影쿬响퓓杂훊质뷸进入죫晶뺧体쳥能쓜力솦?的뗄主훷要튪因틲素쯘。ꆣ?2? ?晶뺧쳥体生짺长뎤벰及粉럛末쒩衍퇜射짤分럖析컶?쪵实验퇩在퓚5??L生짺长뎤槽닛中훐进뷸行탐，ꎬ닉采폃用붵降컂温램法生짺长뎤?KD?P?晶뺧体쳥。ꆣ母쒸液튺由평2?α?)?(?}g?磷쇗酸쯡二뛾氢쟢饵볘试쫔剂볁(??AR?)?，ꎬ4?(?削???mL?电뗧?导떼率싊为캪?1?8?M?{1?'ꆤ?c?m的뗄去좥离샫子ퟓ水쮮和뫍痕뫛量솿金뷰属쫴杂퓓质훊离샫子ퟓ配엤制훆而뛸成돉，ꎬ本놾实쪵验퇩中훐，ꎬ뻟具쳥体쯹所퇐研뺿究뗄的뷰金쫴属샫离子ퟓ主훷要튪有폐???ꆰ22ꎬ??ꆰ뫍???2\Ba+ ，Cu+和Mgꎬ它쯼们쏇以틔B?a?C?1?.ꆤ?2?H?0?ꎬ，C?u?C?1?.ꆤ?2?H?0?和뫍M?g?C?1?.ꆤ?6?H?0?的뗄形탎式쪽加볓人죫，ꎬ一튻般냣认죏为캪，ꎬC?l?-튻在퓚K?D?P?晶뺧?222222体쳥生짺长뎤过맽程돌中훐无컞明쏷显쿔影펰响쿬.ꎮ죜溶液튺탨需要튪经뺭过맽一튻系쾵列쇐的뗄预풤处뒦理샭，ꎬ쫗首先쿈폃用뿗孔径뺶为캪0?.ꎮ1??5?μ?m的뗄싋滤膜쒤뛔对母쒸液튺进뷸行탐超뎬微캢过맽?滤싋，ꎬ좻然뫳后붫将죜溶튺液컂温뛈度퓚在놥饱뫍和컂温뛈度뗄的믹基뒡础上짏提쳡高룟?1?0-ꆫ?1?5?'t뷸:탐进맽行죈过热ꎬ맽，죈过热쪱时볤间돖持탸续?3?6h?，ꎬ틔以돽除좥去죜溶튺液훐中뿉可쓜能存듦?在퓚的뗄聚뻛合뫏体쳥。ꆣ将붫处뒦샭理后뫳的뗄溶죜液튺降붵温컂至훁高룟于폚饱놥和뫍点뗣温컂度뛈?5?'t쪱:쿂时下ퟑ籽뺧晶?(?Z切쟐，ꎬ돟尺寸듧约풼为캪lO??mm?xꇁ 1??0m?m? xꇁ5?m?m?)?。ꆣ?继볌续탸自ퟔ然좻降붵温컂，ꎬ떱当컂温뛈度붵降훁至룟高폚于놥饱和뫍度뛈?1'ꇦt쪱:时뚯转ퟑ动뺧籽晶볜架ꎬ웤，其뺧晶转쯙速뛈度캪为3?0?r?ꎯ/?mi?n，ꎬ基믹本놾程돌序탲为캪左ퟳ转5??0s?ꎬ，춣停????ꎬ폒???ꆣ뿘훆맽놥뫍뛈캪?ꎮ??ꎥ?룹뻝놥뫍뛈쟺쿟???ꎮ??ꇁ???3俨lOs，右转50s。控制过饱和度为毛(根据饱和度曲线S= 4. 04 x 10-+??O.ꎮ 3?6??5?T +? 1?3?.ꎮ 7? ?(g?K?D?P?ꎯI? ?????????11∞mLH、0)[10)?ꎬ，쪹使?KD?P?晶뺧体쳥能쓜够릻快뿬速쯙生짺长뎤。ꆣ?图춼2?담掺入죫?3.ꎮ?05?2?9?ꇁx 1??0 ?-s M??g?C1?2ꆤ.6?H??2?0 ?춼图?1뒿纯첬态뿬快쯙速짺生뎤长?KD?P?뺧晶体쳥照헕片욬?쳵条볾件쿂下뿬快速쯙生짺长뎤?KD?P?뺧晶쳥体照헕片욬???ꎮ??????????????????????????Fig. 1 A photograph of KDP crysta1 ??ꎮ???????????????????????????Fig. 2 A photograph of KDP crystal ?伊g?r?o?w?n? ?w?i?th? ?3ꎮ.0?5?2??9 ꇁx 1??0 튻-?s ?M?g?C?l2? ’ꆤ?6?H?0? ?2늻춬쳵볾쿂뿬쯙짺뎤뗄???뺧쳥죧춼쯹쪾ꎬ듓춼훐뿉틔뾴돶ꎬ담죋???2뫍???2不同条件下快速生长的KDP晶体如图所示，从图中可以看出，掺入Cu+和Mg+쯹所짺生长뎤的뗄晶뺧体쳥与폫纯뒿态첬情쟩?뿶쿂짺뎤뗄뺧쳥쎻폐쏷쿔뗄뫪맛닮뇰ꎻ떫쫇ꎬ담죋???벶뇰뗄???2况下生长的晶体没有明显的宏观差别;但是，掺入10-5级别的Ba+뻍就믡会对뛔晶뺧体쳥外췢观맛产닺生짺明쏷显쿔影펰响쿬，ꎬ듓从图춼?4뿉可?틔以뾴看出돶，ꎬ뺧晶쳥体훹柱쏦面폐有쏷明쿔显的뗄白냗纹컆，ꎬ춬同쪱时ힶ锥훹柱붻交뷧界线쿟也튲能쓜很뫜清쟥楚돾地뗘观맛察달到떽。ꆣ?
캬웕톶 1232 人죋工릤晶뺧体쳥学톧报놨?第뗚3?6?卷뻭????ꆺ????뿚?ꆪ??ꆺ?춼?담죋?ꎮ???ꇁ??ꆫ5图3掺入 1O-C?u?C?1??.ꆤ2?H??0? ?춼?담죋?ꎮ???ꇁ??ꆫ5图4掺入 1O-B?a?C?1??.ꆤ2?H??0? ?2 22 2条쳵볾件下쿂快뿬速쯙生짺长뎤K?D?P?晶뺧体쳥照헕片욬?条쳵件볾下쿂快뿬速쯙生짺长뎤K?D?P?晶뺧体쳥照헕片욬ꎮ???ꎮ???????????????????????????F?? A photograph of KDP crystal ig?ꎮ.4? ?A?? ?ph?o?t?o?gra?p?h? ?o?f ?K?D?P? ?c?r?ys?t?a?l ????????????ꎮ???ꇁ??ꆫ????ꆤ????????????????ꎮ???ꇁ??ꆫ5 gr咽o，wn with 2. 723 x 10 -5 CuCl. 2H0 grown with 1. 145 x 10-B?a?C?I??ꆤ?????.2H0 2 2 22snebdEBA 飞bdEBA10 20 30 40 50 60 70 20!deg. 춼图5?不늻同춬条쳵件볾下쿂?KD?P?晶뺧쳥体的뗄粉럛末쒩衍퇜射짤图춼???ꎮ?????????????????????????????????????????????????ꎺ??????ꎻ??????????????ꎮ???ꇁ???5 Fig.. 5 XRD pattem of KDP crystals grown in different conditions: (a) pure; ( b) doped wii出th x 10-????ꆤ????ꎻ?????????????ꎮ???ꇁ??ꆫ5 MgCl2 .6H0; (c) doped wii出th Xx 10-?B?a?Cl?.ꆤ2?H??0?;ꎻ ?(d?)? d?o??p?ed? ?w?i?出?1??.ꎮ9??6 xꇁ 1??0 ?-?5 ?C?uC?l???.2?H???0 ?22 22 2 为캪了쇋确좷定뚨晶뺧体쳥的뗄结뷡构릹，ꎬ붫将늻不춬同쳵条件볾下쿂的뗄?KD?P?뺧晶体쳥磨쒥成돉粉럛未쒩，ꎬ퓚在日죕놾本阳??ga?k?u?公릫司쮾的뗄型탍号뫅为캪?D/ꎯm?缸???-2?5?∞??粉럛쒩未衍퇜짤射仪틇上짏뷸进行탐粉럛未쒩衍퇜射짤分럖析컶。ꆣ圈춼?5캪为쯹所뗃得到떽的뗄不늻同춬生짺뎤长쳵条볾件쿂下的뗄럛粉未쒩퇜衍射짤图춼比ꎮ뇈较뷏发랢现쿖，ꎬ不늻同춬쳵条件볾쿂下衍퇜?짤射峰럥基믹本놾相쿠同춬，ꎬ쯹所틔以뿉可틔以죏认为캪?K?DP?晶뺧쳥体뷡结릹构并늢不늻因틲为캪本놾文컄所쯹研퇐究뺿的뗄痕뫛量솿的뗄杂퓓质훊阳퇴离샫子ퟓ的뗄加볓入죫而뛸变뇤化뮯。ꆣ??3? 结뷡맻果与폫讨쳖论싛?晶뺧体쳥中훐杂퓓质훊含몬量솿由평等뗈离샫子ퟓ发랢射짤光맢谱웗仪틇(??U?lti?ma??2,ꎬ F?r??a?n?ce?)?닢测定뚨，ꎬ现닢测tl定뚨的뗄部늿位캻分럖别뇰为캪柱훹面쏦和뫍锥ힶ面쏦。ꆣ?K?Hꎺ?P?Û2?4풭쇏훐??ꆰ2ꎬ???2뫍???2몬솿럖뇰캪?ꎮ??ꇁ??튻ꎬ?ꎮ??ꇁ????6뫍?ꎮ???ꇁ???ꆧ6Ba+，Cu+和Mg+含量分别为 10 -6, x 10-原料中和ꆣ?。3?.ꎮ1? 离샫子ퟓ半냫径뺶?훮诸多뛠퇐研究뺿죏认为캪金뷰属쫴离샫子ퟓ半냫径뺶影펰响쿬着ퟅ离샫子ퟓ뷸进入죫?KD?P?뺧晶体쳥的뗄能쓜力솦，ꎬ以틔前잰的뗄研퇐究뺿表뇭明쏷[?1? ꎺ????뛾볛퇴샫ퟓ죧???2????ꎮ?????ꎬ???????ꎮ??????ꎬ???2(1)二价阳离子如Mg+(r = O. 80nm) ,Zn2+ (r = O. 074nm) , Cu+ ?(r? ?=0?.ꎮ ?0?7?2?n?m)?之횮类샠，ꎬ웤其샫离ퟓ子냫半뺶径풼约为캪??K?+ ?(?γ=?0?.ꎮ ?1?3?3?n?m)?的뗄?0.ꎮ5?놶倍，ꎬ튻一냣般살来쮵说，ꎬ샫离ퟓ子틔以쳮填쾶隙랽方쪽式듦存퓚在于폚?K?DP?晶뺧体쳥之횮中훐:ꎻ????뛾볛퇴샫ퟓ죧???2(2)二价阳离子如Pb+?(r? =??0.ꎮ ?1?2?0?n?m?) ,ꎬ?B?i?+ ?(r? ?=?0.ꎮ 1??3?5?n?m)? ꎬ，웤其냫半뺶径폫与?r?냫半径뺶相쿠当떱，ꎬ퇐研뺿究랢发现쿖，ꎬ헢这킩些퇴阳샫离?ퟓ子主훷要튪以틔取좡듺代?r?뗄的탎形式쪽存듦在퓚于폚晶뺧体쳥当떱中훐。ꆣ?뇭?뫍뇭?럖뇰쏨쫶쇋퓚???뺧쳥짺뎤맽돌훐ꎬ쯦ퟅ죜튺훐???2表1和表2分别描述了在KDP晶体生长过程中，随着溶液中Cu+和뫍?B?i?+뗄的늻不뛏断볓加入죫晶뺧쳥体中훐柱훹面쏦和뫍锥ힶ?쏦뗄??ꆧ2벰???2面的Cu+及Ba+含몬量솿及벰其웤变뇤化뮯情쟩况뿶。ꆣ?
캬웕톶 第뗚6?期웚?张헅文컄彬뇲等뗈:ꎺ뛾二볛价퇴阳샫离ퟓ子掺담入죫?KD?P?뺧晶쳥体能쓜力솦的뗄研퇐究뺿?1??2?3?3? 11表1KDP晶体中Cu+含量与其生长溶液中Cu+含量的比较1 Table 1 Comparison between伽econtent of Cu+ ions in伽.ecrystal and tbat in蚀leωlution6C,( X 10-) C, ( x 10 -6) Prisrnatic 1. 94 1. 69 Pyramidal 11表2KDP晶体中Ba+含量与其生长溶液中Ba+含量的比较1 Table 2 Comparison between伽econtent of Ba+ ions in伽ecrystal and伽atin the solution ，.’、LYV3''5吁， 61• 儿C,( X 10-) A'IE3吨'且C, ( x 10 -6) Prismatic 101. 58 A丛TPyramidal 31. 93 2由평짏上述쫶两솽表뇭可뿉知횪:ꎺ튻一方랽面쏦，ꎬ컞无싛论쫇是훹柱面쏦还뮹是쫇锥ힶ面쏦，ꎬ죜溶튺液中훐C?u??+含몬솿量的뗄퓶增加볓늢并不늻明쏷쿔显地뗘랴反映펳在퓚离샫子ퟓ在퓚晶뺧体쳥?훐뗄몬솿짏ꎬ뺧쳥훐뗄퓓훊솿믹놾짏놣듦늻뇤ꎻ폫듋늻춬뗄쫇ꎬ???2中的含量上，晶体中的杂质量基本上保存不变;与此不同的是，Ba+퓚在晶뺧体쳥中훐的뗄솿量随쯦着ퟅ其웤在퓚生짺长뎤溶죜液튺中훐量솿的뗄?增퓶大듳而뛸显쿔著훸增퓶大듳。ꆣ另쇭一튻方랽面쏦，ꎬ붫将훹柱쏦面샫离ퟓ子몬含量솿和뫍锥ힶ面쏦离샫子ퟓ含몬量솿比뇈较뷏发랢现쿖，ꎬ两솽部늿分럖含몬量솿相쿠当떱，ꎬ而뛸뛔对于폚B?a?2ꆧ+，ꎬ훹柱?쏦面离샫子ퟓ含몬量솿明쏷显쿔大듳于폚锥ힶ面쏦。ꆣ?뷡结合뫏本놾实쪵验퇩结뷡果맻与폫前잰人죋的뗄研퇐究뺿，ꎬ컒我쏇们죏认캪为ꎬ，샫离ퟓ子냫半뺶径뗄的늻不춬同펰影쿬响ퟅ着뷰金쫴属퓓杂훊质퇴阳샫离ퟓ子进뷸入죫K?D?P?晶뺧쳥体的뗄能쓜?力솦，ꎬ떱当퓓杂훊质샫离ퟓ子냫半뺶径킡小于폚?K+?半냫径뺶而뛸使쪹得뗃其웤倾쟣向쿲于폚以틔填쳮隙쾶方랽式쪽存듦在퓚于폚K?D?P?뺧晶쳥体中훐时쪱，ꎬ퓓杂훊质샫离ퟓ子쓑难틔以뷸进죫入晶뺧体쳥?且쟒其웤含몬量솿与폫生짺长뎤溶죜液튺中훐杂퓓质훊含몬量솿并늢没쎻有폐明쏷显쿔关맘系쾵，ꎬ同춬时쪱发랢现쿖，ꎬힶ锥훹柱솽两짺生뎤长쏦面뗄的늻不춬同튲也뫜很쓑难랴反펳映在퓚锥ힶ柱훹面쏦上짏的뗄?杂퓓质훊含몬量솿上짏。ꆣ当떱杂퓓质훊离샫子ퟓ半냫径뺶与폫K?+?샫离子ퟓ냫半径뺶相쿠当떱而뛸使쪹其웤쟣倾向쿲于폚以틔取좡代듺?K+?랽方式쪽存듦在퓚于폚?KD?P?晶뺧体쳥中훐时쪱，ꎬ퓓杂훊质?샫ퟓ틗폚뷸죫뺧쳥떱훐쟒웤몬솿쯦짺뎤죜튺훐뗄몬솿퓶듳뛸쏷쿔퓶듳ꎬ훹쏦???2离子易于进入晶体当中且其含量随生长溶液中的含量增大而明显增大，柱面Ba+含몬量솿大듳于폚锥ힶ面쏦，ꎬ컒我쏇们죏认为캪?这헢是쫇由평锥ힶ柱훹两솽生짺长뎤面쏦结뷡构릹不늻同춬造퓬成돉的뗄[?川，ꎬ훹柱쏦面짺生长뎤层닣K?+?和뫍?(?H??P?0??)튻-붻交듭错업排쇐列ꎬ，뛸而ힶ锥쏦面짺生뎤长닣层뷘截횹止于폚?r?，24ꎬ?쯹틔퇴샫ퟓ퓚컼뢽맽돌룼뛠뻛벯퓚훹쏦짏ꎬ뛔폚???2所以阳离子在吸附过程更多聚集在柱面上，对于Cu+及벰将붫튪要提쳡到떽的뗄M?g?2ꆧ+ꎬ，뿉可쓜能웤其쯼它킧效펦应뗖抵쿻消쇋了由평于폚짺生长뎤层닣?不늻同춬而뛸带듸来살的뗄在퓚杂퓓质훊含몬量솿方랽面쏦的뗄影펰响쿬。ꆣ??3ꎮ.2? 쮮水合뫏热죈?S??an?g??w?a?l ?k뗈等人죋퓚在研퇐究뺿金뷰属쫴离샫子ퟓ进뷸入죫?AO?(?A?m?m?o?n?i?um?? ?Ox??a?la?te? M?o?n?o?h?y?d?r?at?e)?뺧晶体쳥能쓜力솦时쪱发랢现쿖[ꆧ叫?，ꎬ샫离ퟓ子的뗄?水쮮合뫏热죈越풽高룟，ꎬ웤其뷸进죫入뺧晶룱格뗄的쓜能솦力뻍就풽越뗍低。ꆣ놾本实쪵퇩验中훐选톡用폃M?g?2ꆰ+，ꎬC??J?\ꎬ拟쓢了쇋解뷢在퓚K?D?P?뺧晶쳥体生짺长뎤过맽程돌中훐，ꎬ쮮水뫏合热죈?쫇是否럱与폫杂퓓质훊阳퇴离샫子ퟓ进뷸入죫晶욷格룱能쓜力솦相쿠关맘??从듓手쫖册닡[ꆧ1?5]훐中뿉可查닩?Ba?C?1?.ꆤ?2?H?0?，ꎬC?u?C?1?ꆤ.?2?H??0和뫍M??g?C?12.ꆤ?6?H?20?的뗄水쮮解뷢?2222죈럖뇰캪??ꎮ????ꆤ???튻I ꎬ??ꎮ?????ꆤ??? ’mol-, kJ. mol-뫍1?3?8?.ꎮ5?3? ?k?J?.ꆤ m?o??l ꆫ-1 0ꆣ 热分别为和?쿂뇭쯹쪾캪쯦ퟅ죜튺훐??2?뗄늻뛏볓죫ꎬ뿬쯙짺뎤돶뗄???뺧쳥훐훹쏦뫍ힶ쏦???2下表所示为随着溶液中Mg+的不断加入，快速生长出的KDP晶体中柱面和锥面Mg+몬含量솿及벰其웤变뇤化뮯情쟩况뿶。ꆣ?表뇭?3??KD?P?晶뺧쳥体中훐M?g?户?含몬量솿与폫其웤生짺长뎤溶죜液튺中훐?Mg?l?+몬含量솿的뗄比뇈较뷏???????????????????????????????????????????1 ??????????????????????????????????????Table 3 Comparison between 甜"ωntentof Mg+ ion in也.ecrystal and伽atin伽eω，Iutionnh4·元筑队"52 523。2 61y•-C,( X 10-) 51. 629 句18。。。，，队3以 Cc ( x 10 -6) Prismatic ukP严田 쪵퇩뷡맻뇭쏷ꎬ뺧쳥훐???2뗄몬솿늢늻쯦ퟅ짺뎤죜튺훐???2实验结果表明，晶体中Mg+的含量并不随着生长溶液中Mg+뗄的含몬量솿的뗄增퓶大듳而뛸增퓶大듳，ꎬ基믹本놾上짏，ꎬ쯼它놣保持돖在퓚?킡폚???뗄컈뚨횵ꎬ춬쪱ힶ훹솽쏦뗄퓓훊몬솿쎻폐쏷쿔뗄듳킡쟸뇰ꆣ폫???2小于10-6的稳定值，同时锥柱两面的杂质含量没有明显的大小区别。与Cu+뗄的情쟩况뿶比뇈较뷏，ꎬ컒我们쏇发랢现쿖，ꎬ컞无싛论是쫇?훹쏦뮹쫇ힶ쏦ꎬ???퓚뺧쳥훐뗄몬솿킡폚???2柱面还是锥面，Mg2+在晶体中的含量小于Cu+퓚在晶뺧体쳥中훐的뗄含몬量솿，ꎬ헢这폫与쮮水合뫏热죈变뇤化뮯趋쟷势쫆类샠似쯆，ꎬ샠类似쯆于폚S?a?n?g?w?a?l??뗈죋뛔뷰쫴샫ퟓ뷸죫??뺧쳥쓑틗뗄뷢쫍ꎬ???쮮뫏죈횵듳폚??2ꆰ뗄ꎬ쯹틔쿠뛔폚??2k等人对金属离子进入AO晶体难易的解释，Mg2+水合热值大于Cu+的，所以相对于Cuꆰ+来살讲붲它쯼更룼难쓑进뷸入죫?晶뺧体쳥内쓚，ꎬ춬同쪱时ꎬ，평由폚于뛾二헟者뗄的샫离ퟓ子냫半뺶径킡小于폚K?+?，ꎬ쯹所틔以쟣倾쿲向틔以쳮填쾶隙랽方쪽式듦存퓚在폚于뺧晶쳥体훐中뛸而떼导훂致뛾二헟者퓚在晶뺧쳥体中훐的뗄量솿?믹基本놾不늻随쯦其웤在퓚生짺长뎤溶죜液튺中훐的뗄量솿改룄变뇤而뛸改룄变뇤。ꆣ??4?结뷡?论싛?本놾文컄目쒿的뗄在퓚于폚寻톰找헒影펰响쿬二뛾价볛阳퇴离샫子ퟓ进뷸入죫?KD?P?晶뺧体쳥쓜能솦力的뗄影펰响쿬因틲素쯘，ꎬ붫将뛾二볛价퇴阳샫离ퟓ子뗄的놾本짭身탔性훊质뫍和其웤掺담入죫?
캬웕톶 1??2?3?4? 人죋工릤晶뺧体쳥学톧报놨?第뗚?36?卷뻭??KD?P?晶뺧쳥体的뗄能쓜솦力联솪系쾵起웰来살。ꆣ研퇐究뺿发랢现쿖:ꎺ샫离ퟓ子냫半뺶径뷏较킡小뗄的퓓杂质훊如죧?CU?Zꆧ+，ꎬM?g?z?+不늻易틗进뷸入죫晶뺧体쳥中훐，ꎬ웤其몬含솿量不늻随쯦所쯹?볓퓓훊솿뇤뮯뛸쿔훸뇤뮯ꎬힶ훹솽늿럖퓓훊몬솿틠닮뇰늻듳ꎻ냫뺶폫??냫뺶쿠떱뗄샫ퟓ죧???2加杂质量变化而显著变化，锥柱两部分杂质含量亦差别不大:半径与K+半径相当的离子如8a+相쿠对뛔来살说쮵更룼?틗易进뷸入죫晶뺧体쳥，ꎬ웤其몬含솿量쯦随쯹所볓加杂퓓质훊量솿增퓶加볓而뛸显쿔著훸增퓶加볓，ꎬힶ锥面쏦杂퓓质훊含몬量솿明쏷显쿔小킡于폚柱훹面쏦的뗄杂퓓质훊含몬量솿.ꎮ同춬时쪱发랢现쿖，ꎬ샫离子ퟓ?的뗄水쮮뫏合热죈越풽高룟，ꎬ웤其퓚在뺧晶쳥体훐中뗄的몬含솿量풽越뗍低ꎮ.ퟜ总뗄的쪵实퇩验뷡结맻果뇭表쏷明ꎬ，샫离ퟓ子냫半뺶径뫍和샫离ퟓ子쮮水뫏合죈热쫇是뻶决뚨定뛾二볛价뷰金쫴属阳퇴离샫子ퟓ?在퓚生짺뎤长过맽程돌中훐进뷸入죫?KD?P?晶뺧体쳥能쓜力솦的뗄重훘要튪因틲素쯘。ꆣ?닎参考뾼文컄献쿗?[?1? ?J D?e? ??Y?or?e?o ?J? ?J ,ꎬB??u?rn?h?a?m?? ?Aꎬ, ?Wh??itm?a?n? ?P? ?K?.ꎮ D??e?v?e?lo?pi?ng?? K?D?P? ?a?n?d?? ?D?KD?P? ?C?ry?s?ta?ls? f?o?r ?th??e ?W?o?r?ld?s ?M?o?st? ?P?ow??e?rf?ul? ?La?s?e??r [?J?J? ꎮ.l?n?t.ꎮ M?a?t?e?r?.ꎮ R??e?v.ꎮ ,ꎬ 2?∞???2ꎬ， ???ꎺ???ꎮ?13: 233. [?2? J? ?N?a?k?at?su?k??a ?M?,ꎬ F??uj?i?ok?a?? ?Kꎬ, ?K?a?n?a?b?e? T?,ꎬ F??uj?i?ta ??H.ꎮ R??a?pi?d? G?r?ow??th? ?o??v?er? 5?0?m?m?ꎯ/?d ?ay? ??o?f ?W??at?e?r-튻s?o?lub?l?e? K?D?P? ?C??ry?s?tal? [?J? ?J .ꎮ ?J.ꎮ C??η?'s?t.ꎮ G?r??o?w仇?，ꎬ?1?9?97?，ꎬ1??71?ꎺ:? ???ꎮ?531. [?3? ?J ?Z?a?its?e?v?a?? ?N? ?P ,ꎬ?et? a?l.ꎮ ?R?ap?i?d? ?Gr?o?wt?h ?o?f? L?a?r?ge?? ?S?ca?l?e (?4?0?-?55??cm??) K?H???P?0?C??ry?s?tal[? ?JJ?.ꎮ ?J.ꎮ ?Cr?y?s?ta?l G??ro?w?thꎬ,1??9?97? ,ꎬ1??8?0:ꎺ 2??5?5.ꎮ? 24 [? 4? ?J ?W?ang? ?K?? P?,ꎬ F?a??ng? ?C? S?,ꎬ e?t? a?l?.ꎮ ?La?s?e?r?-ꆪi?n?d?uc?e?d?? D?a?ma?g??e ?M??e?ch?a?ni?sm??s ?a??n?d ?l?mp?r?ov??em??en??t o?f? O?p??ti?c?al? Q?u??al?iti?es? ?o?f ?Bu??lk?? ?P?o?ta?s?s?iu?m ?D?i?hy??dr?og??en?? P?h??o?s?ph?a??te? C??ry?s?tals? [?J?J?.ꎮ? J. C??ry?s?t?.ꎮ ?G?row?th ，ꎬ2?α??后?，ꎬ2??8?7(?2?)?:ꎺ4?7?8?.ꎮ?[?5?? J N?e?g??re??s ?R? ??A,ꎬ D??e?M?an??ge?? ?P ,ꎬ?D?em??os? ?S?? G?.ꎮ ?ln?v?e?s?t?i?g??at?i?o?n? ?o??f? L?a?s?e?r?? ?A?n?ne??ali?n?g?? P?a??ra??me??t?er??s ?f?o?r ??Op??ti?m??al ??La?s?e??r也ꆪ???ma?g?e???P?er?fo??rm??an?ce? ?i?n?? ?D?eu?t?e??ra??t?ed? ?P?o?t?a?s?s?i?um?? 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