CN1007521B - 掺钕和铈的钇铝石榴石激光晶体的生长技术 - Google Patents

掺钕和铈的钇铝石榴石激光晶体的生长技术

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Publication number
CN1007521B
CN1007521B CN87100530A CN88102651A CN1007521B CN 1007521 B CN1007521 B CN 1007521B CN 87100530 A CN87100530 A CN 87100530A CN 88102651 A CN88102651 A CN 88102651A CN 1007521 B CN1007521 B CN 1007521B
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CN
China
Prior art keywords
yag
crystal
rotating speed
growth
described method
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
Application number
CN87100530A
Other languages
English (en)
Other versions
CN1030798A (zh
Inventor
翟清永
张思远
王庆元
陈朝元
应佐庆
罗魏良
姚光华
肖宗朝
梁泽荣
武士学
孙洪建
石全州
黄昌明
张生秀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South West Institute of Technical Physics
General Motors Co
Original Assignee
South West Institute of Technical Physics
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by South West Institute of Technical Physics filed Critical South West Institute of Technical Physics
Priority to CN87100530A priority Critical patent/CN1007521B/zh
Publication of CN1030798A publication Critical patent/CN1030798A/zh
Publication of CN1007521B publication Critical patent/CN1007521B/zh
Expired legal-status Critical Current

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    • B22D11/06Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0605Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by two belts, e.g. Hazelett-process
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    • B22D11/0637Accessories therefor
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Abstract

本发明涉及掺钕和铈的钇铝石榴石[(Nd,Ce):YAG]激光晶体的引上生长方法,包括组份、加热方法及转速和拉速等生长参数的选取等方面。本发明在不损害晶体光学质量的条件下有效地利用了Ce3+→Nd3+的能量转移。使(Nd,Ce):YAG的脉冲激光效率比优质掺钕钇铝石榴石Nd:YAG提高70%以上,而且具有阈值低,抗紫外辐射能力强,重复频率工作稳定,对环境温度的稳定性和冷却要求低等优点,特别适用于重复频率工作的中小能量脉冲激光器。

Description

本发明涉及掺钕和铈的钇铝石榴石〔(Nd,Ce∶YAG〕激光晶体的引上生长方法。
直到目前为止(Nd∶YAG)单晶仍然是性能优良而且广泛应用的激光晶体。但这种晶体的激光效率不高,为了提高效率,许多科技工作者进行了大量研究。通常采用的也是比较成功的方法是在Nd∶YAG晶体中掺入所谓的敏化离子,利用敏化离子到Nd3+的能量转移来提高泵浦光源的利用率,从而提高Nd∶YAG晶体的激光效率。目前公认的最佳敏化离子是Cr3+,但在YAG晶体中,Cr3+→Nd3+的能量转移效率不高,而且转移时间太长,因此Cr3+的敏化效果不好。特别是在脉冲操作中几乎无明显效果。寻求Nd∶YAG晶体的更佳敏化离子是激光晶体研究中的一个重要课题。
Holloway(1)等最早观察到YAG晶体中Ce3+→Nd3+的能量转移现象。但只是一个现象的观察,并未说明使用样品的情况,对能量转动的机理也未进行讨论。
КОВАЛеВА等(2)在1977年的报导中指出,从Nd3+的荧光激发谱看,对于所用的两个样品而言,掺Ce3+后Nd3+的总荧光强度比Nd∶YAG晶体提高一倍和二倍,因而可以用Ce来敏化Nd∶YAG。但КОВАЛеВА所用的样品是熔体中自发结晶生长的片状单晶,而单晶的尺寸未加说明。其样品的Nd浓度分别为1.4和1.7(wt)%,Ce的浓度分别为0.4和0.8(wt)%。显然КОВАЛеВА所用的掺杂浓度远大于一般激光晶体中的Nd浓度。
Mares(3)在其几篇报导中对YAG晶体中Ce3+→Nd3+的能量转移进行了仔细的研究。所用样品的Nd浓度为0.96(at)%,Ce的浓度为1.4×10-3~2.8×10-2(at)%(据Mares自称,所用样品由Kvapil提供)。Mares指出,Ce与Nd间既存在辐射能量转移,也存在无辐射能量转移。辐射能量转移的效率为14.2%,无辐射能量转移是通过偶极-偶极作用和偶极-四极作用进行的,由于这一过程的发生,Ce3+的荧光寿命从Ce∶YAG的60ns降到双掺的32~39ns。Mares还指出,在低Ce3+浓度情况下,(Ce3+→Ce3+O→Nd3+的多阶过程产生的可能性不大,但Ce3+浓度高时,有产生这种多阶过程的可能。不过,按Jacobs(4)的报导,在高浓度时可能出现Ce3+的激发态吸收。
Kvapil(5)等曾利用掺Ce来改进Nd∶YAG的激光性能。他们认为,虽然在YAG晶体中有Ce3+→Nd3+的能量转移,可以用来提高激光效率,但 能量转移的效率不高,而且大量的Ce掺入会象掺Cr3+一样严重降低晶体的光学质量。因此掺大量的Ce3+来敏化Nd3+的总体使用效益不高。基于这一观点,他们掺Ce3+的目的不是利用Ce3+的敏化作用,而是利用少量Ce3+来抑制Nd∶YAG晶体的瞬时色心和加强不等效晶位Nd3+间的能量转移,从而提高激光效率。Kvapil指出,少量Cr3+掺入,特别是同时掺入少量Ce3+,可以有效地抑制瞬时色心的形成,从而提高连续激光输出。但当Cr3+和Ce3+的浓度高于10-2(at)%时,这种抑制瞬时色心形成的作用减弱和消失。对于脉冲激光输出,掺Ce和Cr的Nd∶YAG与(Nd,Ti)∶YAG类似。
Kvapil报导的(Nd,Ce)∶YAG中Nd的浓度为0.6~0.7(wt)%,Ce的浓度为8×10-4(wt)%、3×10-3(wt)%和2×10-2(at)%。在(Nd,Cr,Ce)∶YAG中Nd和Ce的浓度也是如此。
在〔5〕中没有关于晶体生长的详细报导,但从Kvapil(6)的其他工作看,他们用的是钨加热器,钼锅系统进行引上生长的。在这些报导中,均未说明生长界面的形状,但从对激光棒的选取和加工看,他们的生长界面是凸向熔体的。生长时的保护气氛是98%的Ar和2%的H2
从Kvapil(5)和Mares(3)所给出的激光检测数据看,其(Nd,Ce)∶YAG的连续输出与Nd∶YAG相比无明显改进,而(Nd,Cr,Ce)∶YAG的连续输出比Nd,YAG提高10%左右。
如上所述,在Nd∶YAG中掺Ce可以利用Ce3+→Nd3+的能量转移来提高激光效率,但另一方面,掺Ce也会严重影响晶体的光学质量。本发明的目的就是找出一种恰当的生长(Nd,Ce)∶YAG晶体的方法,使Ce的敏化作用得以充分利用,又可消除或尽量减轻Ce对光学均匀性的损害。从而使(Nd,Ce)∶YAG晶体成为激光性能优于Nd∶YAG而且价格低廉,能广泛推广的实用激光晶体。
本发明是一种(Nd,Ce)∶YAG激光晶体的引上生长法。其中包括粉料的灼烧,配制,混合和成型,然后于坩锅中加热至熔和下籽晶进行旋转引上生长。其特征为按化学式Y3-x-yNdxCeyAl5O12配料;其中x=0.0~0.27,y=5×10-3~0.15;籽晶方向为<111>,<110>,或<211>,晶体直径与坩锅内径比小于1/2;晶体转速为10~150r/min;提拉速度为0.3~3mm/h;保护气氛为还原性或中性气氛。
现将本发明详述如下:
如文献〔1-3〕所述,在YAG晶体中有Ce3+→Nd3+的能量转移。КОВАЛеВА(2)从Nd的荧光激发谱的测量结果中估计,对所用的熔体自发结晶的样品而言,掺Ce后Nd的荧光强度为不掺Ce晶体的2~3倍。而Mares(3)从Ce荧光中Nd3+的吸收而产生的结构估计Ce3+→Nd3+的辐射能量转移效率约为14.2%。除有辐射能量转移外,Mares指出也有Ce3+→Nd3+的无辐射能量转移过程,甚至在Ce浓度高时,还有(Ce3+→Ce3+O→Nd3+的多阶能量转移过程。由这些结果不难看到在YAG中,Ce3+→Nd3+的总能量转移效率可能与Ce3+的浓度有关。另一方面,正如Kvapil(5)所指出,大量的Ce掺入会严重损害晶体的光学质量,其主要原因之一是Ce3+的离子半径比Y3+大,同时也比Nd3+大,因此,在Nd∶YAG中掺入大量Ce,自然会增大应力从而损害晶体的光学质量。总之,从提高能量转移效率而言,希望Ce的浓度高,而从Ce对光学质量的影响看,则要求Ce的浓度愈低愈好。我们认为能量转移效率与光学质量的最佳折衷是与Ce3+/Nd3+的浓度比有关。因此,寻找最佳浓度比是既能充分利用Ce3+→Nd3+的能量转移,又能消除或尽量减轻Ce的危害的重量途径。这也是本发明的一个重要内容。
如所周知,在引上生长中,晶体转速和拉速等生长参数对晶体质量有严重影响。而这些生长参数的最佳值则与熔体组份、加热方式、所用热场、坩锅尺寸及晶体直径等因素有关。例如,拉速过快会产生组份过冷,过慢则由于熔体中的温度振荡使晶体处于过度和过于频繁的生长-回熔-再生长状态下生长而影响晶体质量。对一定系统而言,生长不同直径的晶体拉速也应有相应的调整。因此,不难想到对于一定的生长系统,不同组份的熔体,也应相应地调整生长参数。例如,高Nd浓度和高Ce浓度的熔体,拉速应适当放慢。总之,寻找最佳生长参数是本发明的另一重要内容。
使用的原料最好是高纯的,氧化钇和氧化钕的纯度不低于99.99%,氧化铝的纯度不低于 99.95%分析纯,氧化铈的纯度不低于分析纯,最好是用光谱纯。在称量前,所有原料均需经干燥处理。
经干燥处理的原料按化学式Y3-x-yNdxCeyAl5O12,称量配制,在确定X称Y值时,必须考虑,Nd和Ce在YAG中的分凝系数,按实测或文献报导的Nd分凝系数(0.15~0.20)和Ce的分凝系数(0.124)以及所希望的晶体中Nd和Ce的浓度来确定x和y的大小。x一般为0~0.27,对具体使用来说较佳值为0.09~0.18,y一般为5×10-3~0.15甚至还可以更大些,但从总体效果看,较佳值为0.006~0.04。
称好的原料经研磨混合预压成型,再经1100~1600℃灼烧(也可以不经灼烧)。应该指出,在配料、研磨混合及成型过程中必须严防混入铁和其它杂质。
利用一般引上生长系统进行晶体生长。加热方式可以用电阻加热或感应加热。在使用石墨或钨电阻加热法时,其热场结构的示意图如附图1所示。图中1是钼籽晶杆,2是籽晶,3是晶体,4是熔体,5、6、7是钼上保温屏,8是钼坩锅,9是钼锅托,10、11、12是钼侧保温屏、13是内屏蔽筒、14是电阻加热器、15是托盘、16是电极板、17是钼台罩、18是连接件、19是氧化铝垫片。
在使用感应加热时,其热场结构的示意图如附图2所示。图中1是观察孔,2是拉晶孔,3是籽晶杆,4是籽晶,5是二氧化锆保温罩,6是晶体,7是熔体,8是铱坩锅,9是感应线圈,10是二氧化锆保温沙,11是陶瓷保温筒,12是托盘。
将预压成型的原料置于坩锅中缓慢加热至熔。在利用电阻加热时,使用钼或钨坩锅;在利用感应加热时,使用铱坩锅。待原料充分熔化后,逐渐下降籽晶。籽晶方向是<111>,也可使用<110>、<211>或其它方向的籽晶,但最好是<111>±5°的籽晶。待籽晶接触熔体并稳定后,开始提拉生长。在下籽晶过程中,熔体温度需适当调整。在生长的最初阶段和一般引上生长一样,需经收颈和放肩过程。转入等径生长后,晶体的直径应控制到小于坩锅内直径的1/2,一般为1/2.5~1/4,最好在1/3~1/3.5范围内。
如所周知,引上生长Nd∶YAG晶体时,转速和拉速等生长参数选用得当与否,对晶体的性能有很大影响。由于Ce3+的离子半径比Nd3+和Y3+都大,因此,在生长(Nd,Ce)∶YAG时,生长参数的选用更为重要。例如,转速的大小及其稳定度对晶体生长界面的形状和光学均匀性都有很大影响。本发明所使用的转速在10~150r/min范围内,通过转速的选择,可使晶体生长以凸向熔体的凸界面生长,也可以平界面生长。当选用凸界面生长时,转速一般低于45r/min,如用电阻加热,其较佳值为10~30r/min;用感应加热,其较佳值为10~40r/min。当选用平界面生长时,电阻加热的较佳转速为50~120r/min,感应加热的较佳转速为50~100r/min。至于转速的最佳数值,不仅和生长界面的形状有关,而且与坩锅尺寸和晶体直径有关。一般说来,晶体直径与坩锅直径的比大,转速应低些,比值小转速应高些。应该指出,转速的稳定性也是一个重要因素,特别是平界面生长时,转速的瞬时起伏不得超过±0.5r/min。
提拉速度是另一个重要生长参数。拉速过大会产生组份过冷使晶体报废,拉速过小可能使晶体在过于频繁的生长-回熔-再生长过程中生长,会加重生长条纹应力。拉速的选用应根据所使用的热场情况,掺杂浓度,界面形状和晶体的直径等因素决定。本发明所用的拉速范围是0.3~3.0mm/h,在凸界面生长时,电阻加热的较佳拉速为0.8~1.4mm/h,感应加热的较佳拉速为0.5~1.2mm/h。在平界面生长时,电阻加热的较佳拉速为1.1~2.2mm/h,感应加热的较佳拉速为0.6~1.5mm/h。一般说来,晶体的直径大或掺杂浓度高,拉速应慢;反之,拉速可适当加块。
另一个需要特别说明是生长时的保护气氛。由于掺入Ce,Ce离子可能是三价,也可能是四价,而且四价态更为稳定。具有敏化作用的是三价Ce,因此,生长时的保护气氛应是中性的,但最好是还原性的。本发明用的保护气氛是纯度为4N的Ar,也可用N2或Ar+H2和Ar+N2
在引上生长中,温度控制的重要性是大家熟知的,本发明要求控温精度不低于±0.5℃。
实例1。
按化学式Y3-x-yNdxCeyAl5O12配称原料,其中x=0.12,y=0.06。原料总重为300克。配好的原料置于玛瑙钵中混合1小时,然后装入特制乳胶袋内(共用四层),置于油压机内预压成型。压制 好的料块置于附图1所示的坩锅中,坩锅为钼片冲压而成的Φ60×30mm坩锅,封闭炉门,按通常生长Nd∶YAG晶体的方法抽真空,充Ar气。利用石墨电阻加热元件(如附图1中的14)缓慢加热至完全熔化。逐渐降下籽晶,籽晶方向为<111>±5°。在籽晶下降到液面时,需调整溶体温度使其适于进行引上生长。待籽晶接触熔体后,稳定1小时,然后开始提拉生长。
在生长过程中,转速为80r/min,拉速为2mm/h。等径部分的直径控制为20~23mm。控温精度不低于±0.5℃。
结束生长时,人工提起晶体使其刚好脱离液面。然后停止提拉并缓慢降温,用10小时的时间降至600℃,断电随炉冷至室温,从而结束整个生长过程。
实例2
原料的配制和生长过程与实例1相同,所不同的是转速为15r/min,拉速为1.2mm/h。
其它实例中的原料组份,加热方式,坩锅情况以及生长参数均列于表1中。其它过程与方法和实例1或实例2相同。
应用本发明技术生长的(Nd,Ce)∶YAG晶体,可充分地利用Ce3+→Nd3+的能量转移现象,而且避免或减弱了Ce3+对晶体光学质量的影响。避开小面生长区加工成的Φ3~Φ6的激光棒的消光比大于25dB的超过90%,而且其中绝大部分超过30dB。仅有极少数激光棒的消光比低于20dB〔而且这是由于没有完全避开小面区所致〕。除了在光学均匀性方面能完全满足实用要求外,本发明生长的(Nd,Ce)∶YAG晶体还具有以下优点:
(Nd,Ce)∶YAG晶体的激光效率高。就已达到的结果看,在10焦耳输入时,其静态效率可比1986年全国Nd∶YAG晶体制量评比的获奖棒高70%以上,而且在输入5~6焦耳时约提高一倍。附图3是部分(Nd,Ce)∶YAG晶体的静态脉冲输出与86年全国质量评比获奖的Nd∶YAG(评比编号H510)在同样测试条件下的对比。测试使用的聚光腔为椭圆(2a=24,2b=21mm,腔长70mm,氙灯为Φ5.3×60mm,输出镜反射率为45%,使用的能量计为美国Boulder公司365型。附图3中曲线1~5是(Nd,Ce)∶YAG的静态脉冲输出曲线。激光棒的尺寸1~3是Φ5×80mm,4是Φ5×65mm,5是Φ4×50mm。曲线6是1986年全国Nd∶YAG质量评比获奖的Nd∶YAG的输出曲线(评比编号为H510),棒的尺寸为Φ5×76mm。由图可见,曲线1和2在10焦耳输入时比6的输出高70%以上。
(Nd,Ce)∶YAG晶体的激光阈值明显地低于现在的优质Nd∶YAG棒。从附图3可以看到,(Nd,Ce)∶YAG晶体的激光阈值降低了0.5~1.0焦耳。
(Nd,Ce)∶YAG晶体具有较强的抗紫外辐照能力。利用这种晶体的激光器不需要滤紫外措施。这一特性不仅避免了滤光液等带来的污染,简化了器件,而且可使光源的340nm附近的紫外光能得到有效的利用。
(Nd,Ce)∶YAG晶体没有通常Nd∶YAG晶体的输出衰减现象。我们在19.2焦耳的输入下,以每5秒一次的重复频率连续长时间工作,其每次输出的能量是稳定的。而Nd∶YAG晶体常有明显的逐渐降低现象,严重时可降低20%以上。
(Nd,Ce)∶YAG晶体在重复频率工作下的特性明显优于Nd∶YAG晶体。在简单的风冷条件下,(Nd,Ce)∶YAG晶体的脉冲激光输出随重复频率而下降的速度明显慢于Nd∶YAG晶体。表2是(Nd,Ce)∶YAG晶体与86年全国Nd∶YAG棒质量评比的获奖棒在不同重复频率下输出能量的比较。
表2.(Nd,Ce)∶YAG棒与Nd∶YAG在重复频率下激光输出对比(表见文后)
(Nd,Ce)∶YAG晶体激光输出时环境温度的稳定性强。在强迫闭合风冷条件下,以10次/秒的重复频率工作,当环境温度从30℃上升到100℃时,(Nd,Ce)∶YAG晶体的激光输出能量仅下降5~6%,并可长时间(10分钟以上)工作,在环境温度升到150℃时仍能正常工作。而Nd∶YAG在同样工作条件下,在50℃的环境中工作90秒后就几乎无激光输出。
表1、本发明的其它实例
组份    加热    坩锅    生长参数    备注
x    y    方式    (mm)    转速    拉速
r.p.m    mm/h
实例3    0    0.12    电阻    钼锅φ60×30    80    2
实例4    0    0.12    电阻    同上    15    1.2
实例5    0.12    0.06    电阻    同上    85    2.2
实例6    0.18    0.018    电阻    同上    85    1.5
实例7    0.12    0.006    电阻    同上    85    2.0
实例8    0.12    0.006    感应    铱锅φ90×90    15    1.2
实例9    0.24    0.006    电阻    钼锅φ60×30    80    1.5
实例10    0.15    0.015    电阻    同上    80    2.0
实例11    0.12    0.012    电阻    同上    85    2.8
实例12    0.15    0.015    感应    铱锅φ90×90    80    2.0
参考文献
[1]W.W.Holloway    et.al.,J.Opt.Soc.Am.V59,60,(1969)
[2]Н.С.Ковалева    Н.др.,Ж.Прнк.Спект.Т27,546(1977)
[3]J.A.Marёs;Czech,J.Phyz.B35    883(1985);B36,1079(1986);Rev.Phyz.Appl,V22,145,(1987)
[4]R.R.Jacobs    et.al.,Appl.Phyz.Lett.V33,410(1978)
[5]J.Kvapil    et.al.,Czech.J.Phyz.B34    581(1984)B.Perner    et.al.,捷克专利,240641
[6]J.Kvapil    et.al.,ibid.B29    1282(1979)
[7]J.Kvapil    et.al.,ibid.B23    817(1982)
表2.(Nd,Ce)∶YAG棒与Nd∶YAG在重复频率下激光输出对比
样品    尺寸    2次/秒    5次/秒    10次/秒
(Nd,Ce)∶YAG    φ5×80mm    235mj    234mj    198mj
Nd∶YAG
评比编号H510    φ5×76mm    135mj    125mj    105mj

Claims (9)

1、一种(Nd,Ce)∶YAG激光晶体的引上生长方法,其中包括粉料的灼烧、配制、混合与成型,然后于坩锅中加热至熔后下籽晶,进行旋转引上生长,其特征为:按化学式Y3-x-yNdxCeyAl5O12配料;其中x=0.06~0.24,y=0.006~0.12;使晶体中Nd的浓度为0.4(at)%~1.6(at)%,Ce的浓度为2.5×10-2(at)%~0.5(at)%;籽晶方向为(111)、(110)或(211);晶体直径与坩锅内直径比小于1/2;晶体转速为10~150r/m/n,拉速为0.3~3mm/h;保护气氛为还原性或中性气氛。
2、根据权利要求1所述方法,其特征为采用石墨电阻加热和钼坩锅,以凸界面进行生长;转速为10~40r/m/n,提拉速度为0.8~1.4mm/h。
3、根据权利要求2所述方法,其特征为以平界面进行生长;转速为50~100r/m/n,提拉速度为1.0~2.2mm/h。
4、根据权利要求1所述方法,其特征为采用感应加热和铱坩锅,并以凸界面进行生长;转速为10~40r/m/n,提拉速度为0.5~1.5mm/h。
5、根据权利要求1所述方法,其特征为以平界面进行生长;转速为50~100r/m/n,提拉速度为0.6~1.5mm/h。
6、根据权利要求1所述方法,其特征为采用钨电阻加热和钼坩锅或钨坩锅,以凸界面进行生长;转速为10~40r/m/n,提拉速度为0.8~1.4mm/h。
7、根据权利要求1所述方法,其特征为以平界面进行生长;转速为50~120r/m/n,提拉速度1.0~2.2mm/h。
8、根据上述任一项权利要求所述方法,其特征为籽晶方向为(111)±5°。
9、根据上述任一项权利要求所述方法,其特征为粉料充分研磨均匀,配料前在1000~1350℃下灼烧2~8小时。
CN87100530A 1988-05-09 1988-05-09 掺钕和铈的钇铝石榴石激光晶体的生长技术 Expired CN1007521B (zh)

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CN101338453B (zh) * 2008-07-16 2011-02-16 成都东骏激光股份有限公司 大尺寸无核心yag系列激光晶体的生长方法
US20120020073A1 (en) * 2009-03-23 2012-01-26 Koninklijke Philips Electronics N.V. Optically pumped solid-state laser and lighting system comprising said solid-state laser
CN103469298A (zh) * 2013-08-22 2013-12-25 昆山开威电子有限公司 一种泡生法生长掺铈钇铝石榴石单晶的方法及高温炉
CN104746135B (zh) * 2013-12-27 2017-04-19 成都晶九科技有限公司 一种感应炉平界面大尺寸掺钕钇铝石榴石晶体生长方法
CN104313693B (zh) * 2014-09-19 2017-01-18 北京雷生强式科技有限责任公司 掺杂钇铝石榴石激光晶体的生长装置、晶体生长炉及制备方法
CN106087056B (zh) * 2016-08-03 2019-02-01 成都新源汇博光电科技有限公司 一种针对yag晶体的生长工艺
CN110453284A (zh) * 2018-05-08 2019-11-15 安徽科瑞思创晶体材料有限责任公司 一种gagg闪烁晶体制造方法

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