JPH079998B2 - Cubic boron nitride P-n junction light emitting device - Google Patents
Cubic boron nitride P-n junction light emitting deviceInfo
- Publication number
- JPH079998B2 JPH079998B2 JP160588A JP160588A JPH079998B2 JP H079998 B2 JPH079998 B2 JP H079998B2 JP 160588 A JP160588 A JP 160588A JP 160588 A JP160588 A JP 160588A JP H079998 B2 JPH079998 B2 JP H079998B2
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- junction
- type
- boron nitride
- current
- cubic boron
- Prior art date
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Description
【発明の詳細な説明】 産業上の利用分野 本発明は発光素子に関する。更に詳しくは立方晶窒化ほ
う素を母結晶とした赤外から紫外域の広領域の範囲で発
光し得られる発光素子に関する。TECHNICAL FIELD The present invention relates to a light emitting device. More specifically, the present invention relates to a light emitting device which has cubic boron nitride as a mother crystal and can emit light in a wide range from infrared to ultraviolet.
従来技術 従来、ｐ−ｎ接合型発光素子を形成する素子の素材とし
ては、ひ化ガリウム，燐化ガリウムが知られ実用化され
ている。しかしこれらの発光素子の発光領域は赤外から
緑色の範囲のものである。青色に発光する素子の素材と
してシリコンカーバイド，セレン化亜鉛が開発された
が、シリコンカーバイドでは良質な結晶が得難く、また
セレン化亜鉛ではｐ型結晶が得難いので、ｐ−ｎ接合型
が得難い。そのため未だ実用化されていない。また紫外
域にエネルギーギャップを有する窒化ガリウム，硫化亜
鉛はｐ型を得ることができず、紫外域発光のｐ−ｎ接合
型発光素子は存在していない。2. Description of the Related Art Conventionally, gallium arsenide and gallium phosphide have been known and put to practical use as materials for elements forming a pn junction type light emitting element. However, the light emitting region of these light emitting elements is in the infrared to green range. Silicon carbide and zinc selenide have been developed as materials for devices emitting blue light. However, it is difficult to obtain a good crystal with silicon carbide, and it is difficult to obtain a p-type crystal with zinc selenide, and thus it is difficult to obtain a pn junction type. Therefore, it has not been put to practical use yet. Further, gallium nitride and zinc sulfide having an energy gap in the ultraviolet region cannot obtain a p-type, and there is no p-n junction type light-emitting device emitting light in the ultraviolet region.
発明の目的 本発明は従来のｐ−ｎ接合型発光素子では困難あるいは
不可能であった赤外から紫外域の発光が可能な発光素子
を提供せんとするものである。An object of the present invention is to provide a light emitting device capable of emitting light in the infrared region to the ultraviolet region, which is difficult or impossible with the conventional pn junction type light emitting device.
発明の構成 本発明者らは前記目的を達成すべく鋭意研究の結果、立
方晶窒化ほう素を母結晶としたｐ−ｎ接合型素子のｐ−
ｎ接合部に電流を通すと、赤外から紫外域で発光し、発
光素子として優れたものであることを確認し得た。ま
た、ｐ−ｎ接合部またはｎ側表面に蛍光体を附設すると
任意の発光色に変化させ得られることを知見し得た。こ
れらの知見に基づいて本発明を完成した。As a result of intensive research to achieve the above-mentioned object, the inventors of the present invention have found that the p-n junction device having a cubic boron nitride as a mother crystal has a pn junction type device.
It was confirmed that when an electric current was passed through the n-junction, it emitted light in the infrared to ultraviolet region and was excellent as a light emitting device. Further, it has been found that it is possible to change the emission color to an arbitrary color by attaching a phosphor to the pn junction or the n-side surface. The present invention has been completed based on these findings.
本発明の要旨は、 １）立方晶窒化ほう素を母結晶とし、1mA以上の電流の
通電に耐える少なくとも0.3mm2以上の接合面を有するｐ
−ｎ接合を持った素子からなることを特徴とする1mA以
上の電流の通電により赤外から紫外域で発光し得る発光
素子。The gist of the present invention is as follows: 1) A cubic crystal of boron nitride is used as a mother crystal and has a bonding surface of at least 0.3 mm 2 which can withstand a current of 1 mA or more.
A light-emitting device capable of emitting light in the infrared to ultraviolet region when a current of 1 mA or more is applied, which is composed of a device having an -n junction.
２）立方晶窒化ほう素を母結晶とし、1mA以上の電流の
通電に耐える少なくとも0.3mm2以上の接合面を有するｐ
−ｎ接合を持った素子において、ｐ−ｎ接合部またはｎ
側表面に蛍光体を附設したことを特徴とする1mA以上の
電流の通電により赤外から紫外域で発光し得る発光素
子。2) Cu having a cubic boron nitride as a mother crystal and having a joint surface of at least 0.3 mm 2 or more that can withstand a current of 1 mA or more p
In an element having a −n junction, a pn junction or n
A light-emitting element capable of emitting light in the infrared to ultraviolet region when a current of 1 mA or more is applied, characterized in that a phosphor is attached to the side surface.
にある。It is in.
立方晶窒化ほう素を母結晶にしたｐ−ｎ接合を持つ素子
は次の方法によって製造し得られる。A device having a pn junction in which cubic boron nitride is a mother crystal can be manufactured by the following method.
高圧高温下で密封された例えばモリブデン製容器中に高
温部と低温部を作り、高温部に立方晶BN原料粒とｐ型ま
たはｎ型ドープ材をこれらの溶媒例えば窒化リチウム・
カルシウム（LiCaBN2）溶媒に溶かしたものを入れ、低
温部に前記ドープ材と異なる型の立方晶窒化ほう素結晶
基板を置き温度による溶解差を利用して低温部に置いた
結晶基板上にこれとは異なる伝導型の立方晶窒化ほう素
を析出成長させることによりｐ−ｎ接合のものが得られ
る。容器の圧力、温度は４〜7GPa,1300〜2400℃範囲で
行うことができる。好ましくは5.5GPa,約1700℃であ
る。A high temperature part and a low temperature part are made in, for example, a molybdenum container sealed under high pressure and high temperature, and cubic BN raw material particles and a p-type or n-type doping material are added to these solvents such as lithium nitride.
A solution of calcium (LiCaBN 2 ) dissolved in a solvent was placed, and a cubic boron nitride crystal substrate of a different type from the above-mentioned doping material was placed in the low temperature part, and this was placed on the crystal substrate placed in the low temperature part using the difference in dissolution due to temperature. A pn junction is obtained by depositing and growing cubic boron nitride having a conductivity type different from that of. The pressure and temperature of the container can be 4 to 7 GPa and 1300 to 2400 ° C. It is preferably 5.5 GPa and about 1700 ° C.
ｎ型ドープ材としては例えばシリコン、ｐ型ドープ材と
してはベリリウムが挙げられる。ｐ−ｎ接合面があまり
小さいと発光強度も弱くなるので、0.3平方ミリメータ
はあることが望ましい。母結晶の大きさや形状は制限さ
れず、その形状は塊状結晶でも薄膜結晶のものでもよ
い。このｐ−ｎ接合に電流を流すとｐ−ｎ接合の近傍の
電子と正孔の再結晶によって発光する。電流量がゼロで
あると発光しないが、電流量を増していけば発光強度は
増加し、充分な発光強度を得るには、1mm程度の大きさ
でｐ−ｎ接合を持つ素子においては1mA以上の電流を流
す必要がある。ｐ−ｎ接合に電流を流すにはｐ型部側と
ｎ型部側に電極をつけ、そこから電流を流せばよい。電
流の向きはｐ型からｎ型に流すのが通常であるが、その
逆方向でも発光する。Examples of the n-type doping material include silicon, and examples of the p-type doping material include beryllium. If the pn junction surface is too small, the light emission intensity also weakens, so 0.3 square millimeter is desirable. The size and shape of the mother crystal are not limited, and the shape may be a bulk crystal or a thin film crystal. When a current is applied to the pn junction, light is emitted by recrystallization of electrons and holes near the pn junction. It does not emit light when the amount of current is zero, but the emission intensity increases as the amount of current increases, and in order to obtain sufficient emission intensity, 1mA or more for a device with a pn junction with a size of about 1mm. It is necessary to pass the current. In order to apply a current to the pn junction, electrodes may be attached to the p-type part side and the n-type part side and the current may be applied from there. The direction of current is usually from p-type to n-type, but light is emitted in the opposite direction.
その発光は赤色より長い波長のものだけでなく、赤色か
ら紫外域をも含む領域に亘って発光し得られる。The emission can be emitted not only in a wavelength longer than that of red, but also in a region including red to ultraviolet region.
このｐ−ｎ接合部またはｎ側表面に蛍光体を附設する
と、発光色を変化させることができる。When a phosphor is attached to the pn junction or the n-side surface, the emission color can be changed.
実施例1. ｐ型立方晶窒化ほう素結晶基板の作成 325〜400メッシュの立方晶窒化ほう素の粒子とLiCaBN溶
媒の粉末を、モリブデン製育成容器に（内径4mm、内高3
mm、厚さ1mm）内に詰める。このとき溶媒の中に１重量
％の金属ベリリウム粉末を入れておく。前記モリブデン
製育成容器は高温部と低温部の温度差をつけるように構
成され、高温部を加熱加圧して5.5GPa,1700℃とし20時
間保持する。これにより低温部にｐ型立方晶窒化ほう素
結晶基板が得られた。Example 1. Preparation of p-type cubic boron nitride crystal substrate 325 to 400 mesh cubic boron nitride particles and LiCaBN solvent powder were placed in a molybdenum growth container (inner diameter 4 mm, inner height 3 mm).
mm, thickness 1 mm). At this time, 1% by weight of metal beryllium powder is put in the solvent. The molybdenum growth container is configured to have a temperature difference between a high temperature part and a low temperature part, and the high temperature part is heated and pressurized to 5.5 GPa and 1700 ° C. and held for 20 hours. As a result, a p-type cubic boron nitride crystal substrate was obtained in the low temperature portion.
ｐ−ｎ接合 前記のｐ型立方晶窒化ほう素結晶板を種結晶として育成
容器低温部に置き、前記と同じ立方晶窒化ほう素粒子と
５重量％のシリコン粒を入れたLiCaBN2溶媒粉末とを詰
め、前記と同じ条件下で育成することにより、ｐ型結晶
の上にｎ型単結晶が育成される。このｐ−ｎ接合結晶は
全体が約1mm大の単結晶で、中心部に濃青色のｐ型、周
囲が透明山吹色のｎ型結晶からなるものであった。ｐ−
ｎ接合面の大きさは0.4mm2とした。pn junction The above-mentioned p-type cubic boron nitride crystal plate was placed as a seed crystal in a low temperature part of a growth vessel, and the same cubic boron nitride particles as described above and LiCaBN 2 solvent powder containing 5% by weight of silicon particles were added. And growing under the same conditions as described above, an n-type single crystal is grown on the p-type crystal. This pn junction crystal was a single crystal having a size of about 1 mm as a whole, and consisted of a deep blue p-type crystal in the center and a transparent bright yellow n-type crystal in the periphery. p-
The size of the n-junction surface was 0.4 mm 2 .
第１図に示すように、ｐ−ｎ接合を挟むｐ型部とｎ型部
に銀ペーストの電極４をつけ、ｐ型側を正ｎ型側を負に
して70ボルトの順バイアス電圧をかけると、ｐ型からｎ
型に２ミリアンペアの電流が流れた。銀ペースト電極と
立方晶窒化ほう素半導体との間の電圧降下を除いたｐ−
ｎ接合を挟むｐ型部とｎ型部との間の電圧は間隔約0.2m
mにおいて約５ボルトであった。２ミリアンペアの電流
を通電中に実体顕微鏡でｐ−ｎ接合素子を観察したとこ
ろ、ｐ−ｎ接合部に沿ってその近くのｎ型側に青白い発
光が観察された。As shown in FIG. 1, a silver paste electrode 4 is attached to the p-type part and the n-type part sandwiching the pn junction, and a forward bias voltage of 70 V is applied with the p-type side being positive and the n-type side being negative. And from p-type to n
A current of 2 milliamps passed through the mold. P- excluding the voltage drop between the silver paste electrode and the cubic boron nitride semiconductor
The voltage between the p-type part and the n-type part that sandwich the n-junction is about 0.2 m.
It was about 5 volts at m. When observing the pn junction element with a stereoscopic microscope while applying a current of 2 milliamperes, pale light emission was observed along the pn junction and on the n-type side near the junction.
実施例2. 実施例１における電圧を70ボルトの逆バイアス電圧とし
たところ、ｐ−ｎ接合を挟むｐ型部とｎ型部間の電圧は
−40ボルトで、ｎ型からｐ型に0.5ミリアンペアの電流
が流れ、ｎ型部が橙色に輝いた。Example 2. When the voltage in Example 1 was set to a reverse bias voltage of 70 V, the voltage between the p-type part and the n-type part sandwiching the pn junction was -40 V, and 0.5 mA from n-type to p-type. Current flows, and the n-type part shines orange.
実施例3. 実施例１において流す電流を変化させて発光強度を光度
計で測定したところ、電流量の増加と共に発光強度も増
加した。数ミリアンペア流せば肉眼でも発光を検知し得
られる。Example 3 When the emission intensity was measured with a photometer while changing the current flowing in Example 1, the emission intensity also increased as the amount of current increased. With a few milliamperes, the luminescence can be detected with the naked eye.
実施例4. 実施例１および２の条件下で、発光スペクトルを分光光
度計で測定した。その結果は第２図に示す通りであっ
た。この図は測定系の感度補正を行っていない生のデー
タである。この結果が示すように、2000オングストロー
ムの紫外域から青色にかけても発光することが確認され
た。また電流量の増加と共に短波長へ発光域が拡大され
た。Example 4. Emission spectra were measured with a spectrophotometer under the conditions of Examples 1 and 2. The result was as shown in FIG. This figure is raw data without sensitivity correction of the measurement system. As shown by these results, it was confirmed that light was emitted even from the ultraviolet region of 2000 angstrom to the blue region. In addition, the emission range was expanded to shorter wavelengths as the amount of current increased.
なお、ｐ−ｎ接合を持たないｐ型もしくはｎ型だけの素
子では電流を通じても発光は検知できなかった。It should be noted that light emission could not be detected even through a current in a p-type or n-type element having no pn junction.
実施例5. 実施例１のｐ−ｎ接合部、またはｎ側表面に、銀ドープ
硫化亜鉛，銅ドープ硫化亜鉛，ユーロピウムドープイッ
トリウムオキシサルファイドの蛍光体をそれぞれ塗布
し、ｐ−ｎ接合に順方向の電流を流したところ、それぞ
れ、青色，緑色，赤色の発光が得られた。Example 5 Silver-doped zinc sulfide, copper-doped zinc sulfide, and europium-doped yttrium oxysulfide phosphors were applied to the pn junction or the n-side surface of Example 1, respectively, and the pn junction was forward-oriented. When a current was applied, the blue, green, and red luminescence was obtained, respectively.
発明の効果 本発明は従来の素材を用いたｐ−ｎ接合型発光素子では
得られなかった青色から紫外域の発光を生ずるｐ−ｎ接
合型発光素子を提供し得たものである。更に母結晶が立
方晶窒化ほう素であるため、その熱伝導率，硬度，化学
的安定性においても従来のものに比し優れており、その
ため高温等、あるいは苛酷な条件下でも使用可能である
効果も有する。EFFECTS OF THE INVENTION The present invention can provide a pn junction type light emitting device that emits light in the blue to ultraviolet range, which has not been obtained by a pn junction type light emitting device using conventional materials. Furthermore, since the mother crystal is cubic boron nitride, it has superior thermal conductivity, hardness, and chemical stability as compared with conventional ones, and therefore can be used even at high temperatures or under severe conditions. It also has an effect.
第１図は本発明の発光素子の実施態様図で、第２図は実
施例４で得られた分光スペクトルを示す。 1:n型、2:p型、3:p−ｎ接合面、4:電極。FIG. 1 is an embodiment diagram of a light emitting device of the present invention, and FIG. 2 shows a spectrum obtained in Example 4. 1: n type, 2: p type, 3: pn junction surface, 4: electrode.
Claims (2)
の電流の通電に耐える少なくとも0.3mm2以上の接合面を
有するｐ−ｎ接合を持った素子からなることを特徴とす
る1mA以上の電流の通電により赤外から紫外域で発光し
得る発光素子。1. A device having a pn junction, which has cubic boron nitride as a mother crystal and has a junction surface of at least 0.3 mm 2 and which can withstand a current of 1 mA or more, 1 mA or more. A light-emitting element capable of emitting light in the infrared to ultraviolet region when the current is applied.
の電流の通電に耐える少なくとも0.3mm2以上の接合面を
有するｐ−ｎ接合を持った素子において、ｐ−ｎ接合部
またはｎ側表面に蛍光体を附設したことを特徴とする1m
A以上の電流の通電により赤外から紫外域で発光し得る
発光素子。2. An element having a pn junction, which has a cubic boron nitride as a master crystal and has a junction surface of at least 0.3 mm 2 or more, which can withstand the application of a current of 1 mA or more. 1m characterized by a phosphor attached to the side surface
A light-emitting element that can emit light in the infrared to ultraviolet range when a current of A or higher is applied.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP160588A JPH079998B2 (en) | 1988-01-07 | 1988-01-07 | Cubic boron nitride P-n junction light emitting device |
| US07/388,809 US4980730A (en) | 1987-05-01 | 1989-08-03 | Light emitting element of cubic boron nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP160588A JPH079998B2 (en) | 1988-01-07 | 1988-01-07 | Cubic boron nitride P-n junction light emitting device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01179471A JPH01179471A (en) | 1989-07-17 |
| JPH079998B2 true JPH079998B2 (en) | 1995-02-01 |
Family
ID=11506133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP160588A Expired - Lifetime JPH079998B2 (en) | 1987-05-01 | 1988-01-07 | Cubic boron nitride P-n junction light emitting device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH079998B2 (en) |
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| US9115868B2 (en) | 2011-10-13 | 2015-08-25 | Intematix Corporation | Wavelength conversion component with improved protective characteristics for remote wavelength conversion |
| EP3240052A1 (en) | 2012-04-26 | 2017-11-01 | Intematix Corporation | Methods and apparatus for implementing color consistency in remote wavelength conversion |
| US8994056B2 (en) | 2012-07-13 | 2015-03-31 | Intematix Corporation | LED-based large area display |
| US20140185269A1 (en) | 2012-12-28 | 2014-07-03 | Intermatix Corporation | Solid-state lamps utilizing photoluminescence wavelength conversion components |
| US9217543B2 (en) | 2013-01-28 | 2015-12-22 | Intematix Corporation | Solid-state lamps with omnidirectional emission patterns |
| TWI627371B (en) | 2013-03-15 | 2018-06-21 | 英特曼帝克司公司 | Photoluminescence wavelength conversion components |
| US9318670B2 (en) | 2014-05-21 | 2016-04-19 | Intematix Corporation | Materials for photoluminescence wavelength converted solid-state light emitting devices and arrangements |
| WO2016154214A1 (en) | 2015-03-23 | 2016-09-29 | Intematix Corporation | Photoluminescence color display |
-
1988
- 1988-01-07 JP JP160588A patent/JPH079998B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| ＳＣＩＥＮＣＥ，ＶＯＬ．２３８，（４８２４）（１９８７−１０−９）Ｐ．１８１−１８３ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01179471A (en) | 1989-07-17 |
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