JPH04170397A - Production of gallium nitride thin film - Google Patents
Production of gallium nitride thin filmInfo
- Publication number
- JPH04170397A JPH04170397A JP30039490A JP30039490A JPH04170397A JP H04170397 A JPH04170397 A JP H04170397A JP 30039490 A JP30039490 A JP 30039490A JP 30039490 A JP30039490 A JP 30039490A JP H04170397 A JPH04170397 A JP H04170397A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- raw material
- gallium nitride
- light
- 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.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 229910002601 GaN Inorganic materials 0.000 title claims description 47
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims description 22
- 239000002994 raw material Substances 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 28
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は青色発光ダイオードや青色半導体レーザへの応
用が期待される窒化ガリウム薄膜の製造方法に関し、特
に低温でも高品質の窒化ガリウム薄膜が製造できる方法
に関するものである。[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a method for producing a gallium nitride thin film, which is expected to be applied to blue light emitting diodes and blue semiconductor lasers, and particularly relates to a method for producing a gallium nitride thin film of high quality even at low temperatures. It's about how you can do it.
［従来の技術］
窒化ガリウム（Ｇ ａ Ｎ）は、約３．４ｅＶの広エネ
ルギーギャップをもつ直接遷移型の化合物半導体で青色
から紫外領域にわたる発光素子として有望な材料である
。従来、ＧａＮ薄膜の製造法として有機金属気相成長（
ＭＯＣＶＤ）法が知られている。これは、トリメチルガ
リウム（Ｇａ （ＣＨ））とアンモニア（ＮＨ３）を加
熱した基板（通常、サファイア（α−Ａ１２０３））表
面上で分解１反応させ、ＧａＮ薄膜を製造しようとする
ものである。[Prior Art] Gallium nitride (G a N) is a direct transition type compound semiconductor with a wide energy gap of about 3.4 eV, and is a promising material as a light-emitting element ranging from blue to ultraviolet. Conventionally, metal organic vapor phase epitaxy (
MOCVD) method is known. This is an attempt to manufacture a GaN thin film by subjecting trimethyl gallium (Ga (CH)) and ammonia (NH3) to a decomposition reaction on the surface of a heated substrate (usually sapphire (α-A1203)).
［発明が解決しようとする課題］ しかし、ＮＨ３の分解には高温を要するため。[Problem to be solved by the invention] However, decomposition of NH3 requires high temperatures.
上述の方法では基板温度を９００℃〜１１００℃にする
必要があり、膜中に多数の窒素の空孔が生じ、製造した
ＧａＮ薄膜はそのままでｎ型伝導性を示す薄膜となって
しまい、高低抗のＧａＮ薄膜が得られにくいと言う欠点
があった。このため。In the above method, it is necessary to raise the substrate temperature to 900°C to 1100°C, which creates a large number of nitrogen vacancies in the film, and the produced GaN thin film becomes a thin film that exhibits n-type conductivity as it is. There was a drawback that it was difficult to obtain a thin GaN film. For this reason.
不純物ドープによる伝導性の制御、すなわちｐ型伝導の
ＧａＮ薄膜の製造が困難であった。It has been difficult to control conductivity by doping impurities, that is, to manufacture p-type conductive GaN thin films.
本発明は窒素の空孔が少なく、高低抗で、不純物ドープ
により容易にｎ型伝導性ないしはｎ型伝導性の薄膜にし
得る伝導性制御の可能なＧａ’Ｎ薄膜の製造方法を提供
することを目的とするものである。The present invention provides a method for producing a Ga'N thin film with few nitrogen vacancies, high and low resistance, and which can be easily made into an n-type conductive or n-type conductive thin film by doping with impurities and whose conductivity can be controlled. This is the purpose.
［課題を解決するための手段］
本発明では前記課題を解決するために９次の構成を有す
るものである。[Means for Solving the Problems] In order to solve the above problems, the present invention has a nine-order configuration.
（１）基板表面にガリウムを含む原料及び窒素を含む原
料を供給しつつ前記基板表面に光を照射して窒化ガリウ
ム薄膜を製造する方法において、前記ガリウムを含む原
料の供給を間欠的に行なうことを特徴とする窒化ガリウ
ム薄膜の製造方法。(1) In the method of manufacturing a gallium nitride thin film by irradiating light onto the substrate surface while supplying a raw material containing gallium and a raw material containing nitrogen to the substrate surface, the raw material containing gallium is supplied intermittently. A method for producing a gallium nitride thin film characterized by:
（２）窒素を含む原料がアンモニアであり、光が波長２
００ｎｍ以下の光を含む光である前記１項に記載の窒化
ガリウム薄膜の製造方法。(2) The raw material containing nitrogen is ammonia, and the light has a wavelength of 2
2. The method for producing a gallium nitride thin film according to item 1 above, wherein the light includes light of 00 nm or less.
（３）窒化ガリウム薄膜製造中の基板の温度が５００℃
〜７５０℃である前記１項に記載の窒化ガリウム薄膜の
製造方法。(3) The temperature of the substrate during gallium nitride thin film production is 500℃
The method for producing a gallium nitride thin film according to item 1 above, wherein the temperature is 750°C.
（４）窒化ガリウム薄膜製造中に更にＳｅ、Ｓｉ。(4) Se and Si are further added during the production of gallium nitride thin film.
ＧｅまたはＳｎを含む原料から選ばれた少なくとも１種
を基板表面に供給する前記１〜３項のいずれかに記載の
窒化ガリウム薄膜の製造方法。4. The method for producing a gallium nitride thin film according to any one of items 1 to 3 above, wherein at least one selected from raw materials containing Ge or Sn is supplied to the substrate surface.
（５）窒化ガリウム薄膜製造中に更にＣｄ、Ｂｅ。(5) Cd and Be are added during the production of gallium nitride thin film.
Ｍｇ、ＺｎまたはＬｉを含む原料から選ばれた少なくと
も１種を基板表面に供給する前記１〜３項のいずれかに
記載の窒化ガリウム薄膜の製造方法。4. The method for producing a gallium nitride thin film according to any one of items 1 to 3 above, wherein at least one material selected from raw materials containing Mg, Zn, or Li is supplied to the substrate surface.
［作 用コ 本発明では、ＧａＮ薄膜を製造する場合、まず。[Production use] In the present invention, when manufacturing a GaN thin film, first.
加熱された基板表面にガリウム原料及び窒素原料を同時
に供給しつつ光を基板表面に照射してＧａＮ薄膜を形成
する。このままでは、ＧａＮ薄膜中まだ多数の窒素の空
孔が存在する。このため、その後、ガリウム原料の供給
をいったん打ち切り。A GaN thin film is formed by irradiating light onto the heated substrate surface while simultaneously supplying a gallium raw material and a nitrogen raw material to the heated substrate surface. If this continues, many nitrogen vacancies will still exist in the GaN thin film. As a result, the supply of gallium raw materials was temporarily discontinued.
窒素原料のみが基板表面に供給される状態を作り。Create a condition where only nitrogen raw material is supplied to the substrate surface.
この間に基板表面に照射された光により窒素原料が分解
され、生成した窒素原子がＧａＮ膜中の窒素の空孔を補
う。このように光を照射しながらのＧａＮ薄膜の形成と
ＧａＮ薄膜中の窒素の空孔への窒素の充填とを交互に繰
り返すことによって従来のＭＯＣＶＤ法よりは低温で窒
素の空孔の少い高抵抗のＧａＮ薄膜が製造でき、不純物
ドープにより伝導性の制御が可能となる。During this time, the nitrogen raw material is decomposed by the light irradiated onto the substrate surface, and the generated nitrogen atoms fill the nitrogen vacancies in the GaN film. In this way, by alternately repeating the formation of a GaN thin film while irradiating light and the filling of nitrogen vacancies in the GaN thin film, it is possible to create a high temperature film with fewer nitrogen vacancies at a lower temperature than the conventional MOCVD method. A resistive GaN thin film can be manufactured, and its conductivity can be controlled by doping with impurities.
また、第２の発明においては、アンモニアを用い２００
ｎｍ以下の波長の光を含む光を照射するので、より窒素
原料の分解、反応が容易になる。In addition, in the second invention, ammonia is used to
Since light including light having a wavelength of nm or less is irradiated, the decomposition and reaction of the nitrogen raw material becomes easier.
第３の発明においては、従来法よりはるかに低温で製造
するにもかかわらず、得られる薄膜の結晶性は低下せず
、また、低温で製造できるので、窒素の空孔がより少な
くできる。In the third invention, although the thin film is manufactured at a much lower temperature than the conventional method, the crystallinity of the obtained thin film does not deteriorate, and since the thin film can be manufactured at a low temperature, the number of nitrogen vacancies can be further reduced.
第４の発明においてはＳｅ、 Ｓｊ、 Ｇｅ、 Ｓ
ｎなどを含む原料を用いてドープされるので、容易にｎ
型導電性の薄膜を得ることができる。In the fourth invention, Se, Sj, Ge, S
Since it is doped using a raw material containing n, etc., it is easy to dope with n.
A type conductive thin film can be obtained.
また、第５の発明においてはＣｄ、 Ｂｅ、 Ｍｇ。Further, in the fifth invention, Cd, Be, Mg.
Ｚｎ、Ｌｉなどを含む原料を用いてドープされるので、
容易にｐ型導電性の薄膜を得ることができる。Since it is doped using raw materials containing Zn, Li, etc.
A p-type conductive thin film can be easily obtained.
［実施例コ 以下２本発明を実施例により詳細に説明する。[Example code] The present invention will be explained in detail below using two examples.
第１図は本発明の製造方法の一実施例で用いられる光Ｃ
ＶＤ装置の構造を示す概略図である。同図において、１
は真空容器、２は真空ポンプ、３は基板、４は基板ホル
ダ、５はヒータ、６ａはＧａ（ＣＨ３）３ガスボンベ、
６ｂはＮＨ３ガスボンベ、５ｃはＨ２ガスガスボンベ、
７ａ、 ｂ、 ｃはマスフローコントローラ、
８ａ、ｂ、ｃはノズル、９はＨｇランプ、１０ａ、ｂ、
ｃはＨｇランプ光、１１はコリメータ、１２はハーフミ
ラ−９１３はパワーメータ、１４は合成石英などからな
る窓である。Figure 1 shows the light C used in one embodiment of the manufacturing method of the present invention.
1 is a schematic diagram showing the structure of a VD device. In the same figure, 1
is a vacuum container, 2 is a vacuum pump, 3 is a substrate, 4 is a substrate holder, 5 is a heater, 6a is a Ga(CH3)3 gas cylinder,
6b is an NH3 gas cylinder, 5c is an H2 gas cylinder,
7a, b, c are mass flow controllers,
8a, b, c are nozzles, 9 is an Hg lamp, 10a, b,
11 is a collimator, 12 is a half mirror, 913 is a power meter, and 14 is a window made of synthetic quartz or the like.
実際の薄膜成長は次のような手順で行なう。まず表面を
清浄にした基板３を基板ホルダ４に装着する。本実施例
では基板３はα−Ａ１２０３を用いた。次に真空容器１
を真空ポンプ２により例えば１０’Ｔｏｒｒ以下程度の
高真空まで排気する。Actual thin film growth is performed in the following steps. First, the substrate 3 whose surface has been cleaned is mounted on the substrate holder 4. In this example, α-A1203 was used as the substrate 3. Next, vacuum container 1
is evacuated by the vacuum pump 2 to a high vacuum of, for example, 10' Torr or less.
次に基板３をヒータ５により結晶成長に適切な温度にす
る。本実施例では７００℃とした。次にＨｇランプ９を
点灯する。Ｈｇランプ光１０ａはコリメータ１１により
平行光にされ、その後、ハーフミラ−１２により同強度
の二つの光１０ｂ、１０ｃとなり、光１０ｂは窓１４を
通って基板３に照射される。光１０ｃの強度をパワーメ
ータ１３により測定することにより基板３に照射される
光１０ｂの強度を知ることができる。光１０ｂの強度を
Ｈｇランプ９を調節することにより、薄膜成長及びＮＨ
３の分解に必要な強度にする。本実施例では３０ ｍＷ
／ ｃ ｍ ２とした。次にＧａ （ＣＨ３）３ガスボ
ンベ６ａ及びＮ Ｈ３ガスボンベ６ｂから供給される夫
々の原料ガスの流量をマスフローコントローラ７ａ、ｂ
により適当な流量比になるよう調節し、ノズル８ａ、ｂ
により基板３表面に供給する。また、同時にノズル８Ｃ
よりＨ２ガスボンベ６Ｃから供給されるＨ２ガスを真空
容器１内に導入する。本実施例における流量は、 Ｇａ
（ＣＨ３）３ガスがＱ、４５ｓｅｃｍ、ＮＨ３ガスが２
７０ｓｅｃｍ、Ｈ，、ガスが５０ｓｅｃｍとした。用い
たＨｇランプ光の分光分布図は第２図に示すとおりであ
り、用いた原料であるＧａ（ＣＨ３）３ガス及びＮＨ３
ガス分子の気相中での吸収帯は２０．０ｎｍ以下にある
ので、光は原料の分解９反応を促進して低温においても
結晶性の良好なＧａＮ薄膜が形成できる。しかしながら
、この状態においても、まだ、多数の窒素の空孔が存在
するので、Ｇａ （ＣＨ３）３ガスの供給をいったん止
め、ＮＨ３ガスのみ（この場合、Ｈ２ガスは流しても流
さな（でもよい）が基板３表面に供給される状態にして
、基板３表面に照射されるＨｇランプ光１０ｂによるＮ
Ｈ３ガス分子の分解により生成された窒素原子でＧａＮ
膜中の窒素の空孔を補う操作を行なう。このように光を
照射しながらのＧａＮ薄膜の形成とＧａＮ薄膜中の窒素
の空孔への窒素の充填とを交互に繰り返すことによって
ＧａＮ薄膜を製造した。なお、Ｇａ （ＣＨａ ）３ガ
スの供給時間と非供給時間の比率は本実施例では１：１
０とした。Next, the substrate 3 is brought to a temperature suitable for crystal growth using the heater 5. In this example, the temperature was set at 700°C. Next, the Hg lamp 9 is turned on. The Hg lamp light 10a is made into parallel light by a collimator 11, and then turned into two lights 10b and 10c of the same intensity by a half mirror 12. The light 10b passes through a window 14 and is irradiated onto the substrate 3. By measuring the intensity of the light 10c with the power meter 13, the intensity of the light 10b irradiated onto the substrate 3 can be determined. By adjusting the intensity of the light 10b using the Hg lamp 9, thin film growth and NH
Make the strength necessary for disassembly in step 3. In this example, 30 mW
/cm2. Next, the flow rates of the raw material gases supplied from the Ga (CH3)3 gas cylinder 6a and the N H3 gas cylinder 6b are controlled by the mass flow controllers 7a, b.
The nozzles 8a and b are adjusted to have an appropriate flow rate ratio.
is supplied to the surface of the substrate 3. Also, at the same time, nozzle 8C
Then, H2 gas supplied from the H2 gas cylinder 6C is introduced into the vacuum container 1. The flow rate in this example is Ga
(CH3)3 gas is Q, 45sec, NH3 gas is 2
70 sec, H, gas was 50 sec. The spectral distribution diagram of the Hg lamp light used is as shown in Figure 2.
Since the absorption band of gas molecules in the gas phase is below 20.0 nm, light promotes the decomposition 9 reaction of the raw material, and a GaN thin film with good crystallinity can be formed even at low temperatures. However, even in this state, there are still many nitrogen vacancies, so the supply of Ga (CH3)3 gas is temporarily stopped, and only NH3 gas (in this case, H2 gas may or may not be supplied). ) is supplied to the surface of the substrate 3, and N by the Hg lamp light 10b irradiated onto the surface of the substrate 3.
GaN is formed by nitrogen atoms generated by decomposition of H3 gas molecules.
An operation is performed to compensate for nitrogen vacancies in the membrane. A GaN thin film was manufactured by alternately repeating the formation of a GaN thin film while irradiating light and the filling of nitrogen vacancies in the GaN thin film with nitrogen. Note that the ratio of the supply time and non-supply time of Ga (CHa)3 gas is 1:1 in this example.
It was set to 0.
以上のような方法で製造したＧａＮ薄膜は、従来のＭＯ
ＣＶＤ法に比べて数百℃以上も低い７００℃という基板
温度で製造したにもかかわらず窒素の空孔などの格子欠
陥のない極めて良質な単結晶膜となり、不純物ドープに
よる伝導゛性制御の可能な高抵抗の電気的性質を示し、
また優れた光学的性質を示した。また、ＧａＮ薄膜製造
中にＣｄ。The GaN thin film produced by the method described above is different from the conventional MO
Even though it was manufactured at a substrate temperature of 700°C, which is several hundred degrees lower than that of the CVD method, the resulting single-crystal film is of extremely high quality without lattice defects such as nitrogen vacancies, and conductivity can be controlled by doping with impurities. It exhibits high resistance electrical properties,
It also showed excellent optical properties. In addition, Cd was added during the production of GaN thin films.
Ｂｅ、Ｍｇ、Ｚｎ、Ｌｉの内の１種類を含む原料気体分
子を基板表面に供給することによってｐ型伝導のＧａＮ
薄膜（キャリヤ密度１０１８以上）が製造できることを
、また、ＧａＮ薄膜製造中にＳｅ、Ｓｉ、Ｇｅ、Ｓｎの
内の１種類を含む原料気体分子を基板表面に供給するこ
とによってｎ型伝導のＧａＮ薄膜（キャリヤ密度１０１
８以上）が製造できることを確認した。GaN with p-type conduction is produced by supplying raw material gas molecules containing one of Be, Mg, Zn, and Li to the substrate surface.
It was also shown that a thin film (carrier density of 1018 or more) can be produced by supplying raw material gas molecules containing one of Se, Si, Ge, and Sn to the substrate surface during GaN thin film production. (Carrier density 101
8 or higher) was confirmed to be able to be manufactured.
なお上述の実施例では、Ｈ２ガスを用いたが。Note that in the above embodiment, H2 gas was used.
必ずしも必要ではない。しかし、Ｈ２ガスは反応の促進
とＧａＮ薄膜へ中の炭素原子の混入を防ぐ効果があり、
用いると好ましい。Not necessarily necessary. However, H2 gas has the effect of accelerating the reaction and preventing carbon atoms from entering the GaN thin film.
It is preferable to use it.
また２本発明で用いられるガリウムを含む原料としては
Ｇａ （ＣＨ３）３のはかＧａ （Ｃ２Ｎ５ ）３など
が用いられ、上述の例に限られるものではない。Further, the raw material containing gallium used in the present invention includes Ga (CH3)3, Ga (C2N5)3, etc., and is not limited to the above-mentioned examples.
本発明で用いられる窒素を含む原料としては、ＮＨ３の
ほか、Ｎ ２ Ｈｉ、やＮ２など各種の窒素含有化合物
を用いることができる。As the nitrogen-containing raw material used in the present invention, in addition to NH3, various nitrogen-containing compounds such as N2Hi and N2 can be used.
また、基板としてα−Ａ１２０３のほか、例えばＧａＡ
ｓ、Ｓｉ、ＳｉＣ等他の基板を用いてもよい。In addition to α-A1203 as a substrate, for example, GaA
Other substrates such as S, Si, and SiC may also be used.
さらに、光源はＨｇランプに限らず、波長が原料ガス分
子の分解に適当なものであれば同様の効果が得られる。Furthermore, the light source is not limited to an Hg lamp, and the same effect can be obtained as long as the wavelength is suitable for decomposing raw gas molecules.
例えば、その他の光源の具体例としては、重水素ランプ
、エキシマレーザ（Ａ ｒ Ｆ）などが挙げられる。For example, specific examples of other light sources include a deuterium lamp, an excimer laser (A r F), and the like.
また、薄膜製造中の基板温度は、５００℃以上７５０°
Ｃ以下が好適である。この範囲内では、窒素の充填時間
が極めて長くなるような欠点がなく、ＧａＮのＮ原子の
空孔が少なく良好な結晶性の膜が得られる。In addition, the substrate temperature during thin film production is 500°C or higher and 750°C.
C or less is preferable. Within this range, there is no drawback that the nitrogen filling time becomes extremely long, and a film with good crystallinity with few vacancies of N atoms in GaN can be obtained.
なお前記ＧａＮ薄膜形成中の圧力は、７６０Ｔ。Note that the pressure during the formation of the GaN thin film was 760T.
「ｒ〜ｌ Ｔｏｒｒ程度が好適である。"A level of approximately r to l Torr is suitable.
また、照射する光の強度については光源の種類や原料化
合物の種類などによって変わるが、−船釣には１０ｍＷ
／Ｃｍ 〜ＩＷ／Ｃｍ２、好ましくは１００ｍＷ／ｃｍ
〜５００ｍＷ／ｃｍ２の範囲が用いられる。In addition, the intensity of the irradiated light varies depending on the type of light source and the type of raw material compound, but - for boat fishing it is 10mW.
/Cm ~ IW/Cm2, preferably 100mW/cm
A range of ~500 mW/cm2 is used.
原料ガスの流量の割合については、体積基準でガリウム
を含む原料、１に対し、窒素を含む原料が５００〜５０
００好ましくは８００〜１２００程度であり、更にＨ２
ガスを用いる場合には、ガリウムを含む原料に１に対し
て１０〜１２０の割合で用いるのが一般的である。Regarding the ratio of the flow rate of the raw material gas, on a volume basis, the raw material containing gallium is 1 to 500 to 50 for the raw material containing nitrogen.
00 is preferably about 800 to 1200, and H2
When using a gas, it is generally used in a ratio of 10 to 120 parts per part of the raw material containing gallium.
ガリウムを含む原料の供給時間と非供給時間の割合は、
各種の条件によって異なってくるが、例えば、１：５〜
１：１００、好ましくは１：８〜１：２０である。The ratio of supply time and non-supply time of raw materials containing gallium is
Although it varies depending on various conditions, for example, 1:5 ~
The ratio is 1:100, preferably 1:8 to 1:20.
Ｓｅ、Ｓｉ、Ｇｅ、Ｓｎなどを含む原料を用いてドープ
を行なう場合のこれらの原料としては、例えば５ｅＨＲ
（但し、Ｒは炭素数１〜４ ２−ｎ
のアルキル基、ｎは０〜２の整数を表す。）で示される
化合物や、５ｉＨＲ（但し、Ｒは炭 ４−ｎ
素数１〜４のアルキル基、ｎは０〜４の整数を表す。）
で示される化合物、ＧｅＨＲ（但し、 ４−ｎ
Ｒは炭素数１〜４のアルキル基、ｎはＯ〜４の整数を表
す。）で示される化合物、Ｓｎ ＨＩＩＲ４−ｎ（但し
、Ｒは炭素数１〜４のアルキル基、ｎは０〜４の整数を
表す。）で示される化合物など、水素化物やアルキル化
物などが挙げられる。When doping is performed using raw materials containing Se, Si, Ge, Sn, etc., examples of these raw materials include 5eHR.
(However, R is an alkyl group having 1 to 4 2-n carbon atoms, and n is an integer of 0 to 2.) group, n represents an integer from 0 to 4.)
Compounds represented by GeHR (4-n R is an alkyl group having 1 to 4 carbon atoms, n is an integer of 0 to 4), Sn HIIR4-n (R is a carbon number 1-4 alkyl group, n represents an integer of 0-4), hydrides, alkylated products, and the like.
Ｃｄ、Ｂｅ、Ｍｇ、Ｚｎ、Ｌｉなどを含む原料を用いて
ドープを行なう場合のこれらの原料としては、例えばＣ
ｄＨＲ（但し、Ｒは炭素数 ２−ｎ
１〜４のアルキル基、ｎはＯ〜２の整数を表す。）で示
される化合物や、ＢｅＨＲ（但し、Ｒｎ ２−［＋
は炭素数１〜４のアルキル基、ｎは０〜２の整数を表す
。）で示される化合物、ＭｇＨ，Ｒ，Ｉｌ（ただし、Ｒ
は炭素数１〜４のアルキル基、ｎは０〜２の整数を表す
。）で示される化合物、ＺｎＨＲ（但し、Ｒは炭素数１
〜４のアルキル ２−ｎ
基、ｎは０〜２の整数を表す。）で示される化合物、Ｌ
ｉＨ，ＬｉＲ（但し、Ｒは炭素数１〜４のアルキル基を
表す。）で示される化合物など、水素化物やアルキル化
物などが挙げられる。When doping is performed using raw materials containing Cd, Be, Mg, Zn, Li, etc., examples of these raw materials include Cd, Be, Mg, Zn, Li, etc.
Compounds represented by dHR (where R is an alkyl group having 2-n 1 to 4 carbon atoms, and n is an integer of 0-2) and BeHR (where Rn 2-[+ is an alkyl group having 1 to 4 carbon atoms); alkyl group, n represents an integer of 0 to 2), MgH, R, Il (however, R
represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 2. ), ZnHR (where R is 1 carbon number)
-4 alkyl 2-n groups, n represents an integer of 0-2. ), a compound represented by L
Examples include compounds represented by iH and LiR (wherein R represents an alkyl group having 1 to 4 carbon atoms), hydrides, alkylated products, and the like.
これらのドープ量は、用いる原料の種類や、目的とする
電導度によって異なるが、目安としては、キャリヤ密度
で１０〜１０１９程度である。The amount of doping varies depending on the type of raw material used and the desired conductivity, but as a guideline, the carrier density is about 10 to 1019.
［発明の効果］
以上述べてきたように９本発明によれば、窒素原子の空
孔のない高抵抗のＧａＮ薄膜を製造することができる。[Effects of the Invention] As described above, according to the present invention, a high-resistance GaN thin film without nitrogen atom vacancies can be manufactured.
また、本発明は不純物ドープによる伝導性制御が可能な
ＧａＮ薄膜の製造方法を提供でき、青色発光ダイオード
や青色半導体レーザ製造に極めて有用である。Further, the present invention can provide a method for manufacturing a GaN thin film whose conductivity can be controlled by doping with impurities, and is extremely useful for manufacturing blue light emitting diodes and blue semiconductor lasers.
更に、第２の発明においては、アンモニアを用い２００
ｎｍ以下の波長の光を含む光を照射するので、より窒素
原料の分解、反応が容易になる。Furthermore, in the second invention, using ammonia, 200
Since light including light having a wavelength of nm or less is irradiated, the decomposition and reaction of the nitrogen raw material becomes easier.
第３の発明においては、従来法よりはるかに低温で製造
するにもかかわらず、得られる薄膜の結晶性は低下せず
、また、低温で製造できるので、窒素の空孔がより少な
くできる。In the third invention, although the thin film is manufactured at a much lower temperature than the conventional method, the crystallinity of the obtained thin film does not deteriorate, and since the thin film can be manufactured at a low temperature, the number of nitrogen vacancies can be further reduced.
第４の発明においてはＳｅ、Ｓｉ、Ｇｅ、Ｓｎなどを含
む原料を用いてドープされるので、容易にｎ型導電性の
薄膜を得ることができる。In the fourth invention, since the material is doped using a raw material containing Se, Si, Ge, Sn, etc., an n-type conductive thin film can be easily obtained.
また、第５の発明においてはＣｄ、Ｂｅ、Ｍｇ。Moreover, in the fifth invention, Cd, Be, Mg.
Ｚｎ、Ｌｉなどを含む原料を用いてドープされるので、
容易にｐ型導電性の薄膜を得ることができる。Since it is doped using raw materials containing Zn, Li, etc.
A p-type conductive thin film can be easily obtained.
第１図は本発明の一実施例で用いられる光ＣｖＤ装置の
構造を示す概略図、第２図は本発明の一実施例で用いら
れるＨｇランプの分光分布図である。
１・・・真空容器、 ２・・・真空ポンプ、 ３・
・・基板。
４・・・基板ホルダ、 ５・・・ヒータ、 ６ａ
・・・Ｇａ（ＣＨ） ガスボンベ、 ６ｂ・・・
ＮＨ３ガスボンベ、 ５ｃ＝・Ｈ２ガスボンベ、７
ａ、ｂ、ｃ・・・マスフローコントローラ、８ａ、ｂ、
ｃ・・・ノズル、 ９・Ｈｇランプ、 １０ａ
、ｂ、ｃ−・Ｈｇランプ光、 １１・・・コリメータ
、 １２・・・ハーフミラ−１１３・・・パワーメー
タ、 １４・・・窓。
１４・・・思FIG. 1 is a schematic diagram showing the structure of an optical CvD device used in an embodiment of the present invention, and FIG. 2 is a spectral distribution diagram of an Hg lamp used in an embodiment of the present invention. 1... Vacuum container, 2... Vacuum pump, 3.
··substrate. 4... Substrate holder, 5... Heater, 6a
...Ga(CH) gas cylinder, 6b...
NH3 gas cylinder, 5c=・H2 gas cylinder, 7
a, b, c...mass flow controller, 8a, b,
c... Nozzle, 9.Hg lamp, 10a
, b, c--Hg lamp light, 11... Collimator, 12... Half mirror 113... Power meter, 14... Window. 14... Thoughts
Claims (5)
料を供給しつつ前記基板表面に光を照射して窒化ガリウ
ム薄膜を製造する方法において、前記ガリウムを含む原
料の供給を間欠的に行なうことを特徴とする窒化ガリウ
ム薄膜の製造方法。(1) In the method of manufacturing a gallium nitride thin film by irradiating light onto the substrate surface while supplying a raw material containing gallium and a raw material containing nitrogen to the substrate surface, the raw material containing gallium is supplied intermittently. A method for producing a gallium nitride thin film characterized by:
００ｎｍ以下の光を含む光である請求項１に記載の窒化
ガリウム薄膜の製造方法。(2) The raw material containing nitrogen is ammonia, and the light has a wavelength of 2
2. The method for producing a gallium nitride thin film according to claim 1, wherein the light includes light of 00 nm or less.
〜７５０℃である請求項１に記載の窒化ガリウム薄膜の
製造方法。(3) The temperature of the substrate during gallium nitride thin film production is 500℃
The method for producing a gallium nitride thin film according to claim 1, wherein the temperature is 750°C.
またはＳｎを含む原料から選ばれた少なくとも１種を基
板表面に供給する請求項１〜３のいずれかに記載の窒化
ガリウム薄膜の製造方法。(4) Se, Si, and Ge are added during the production of gallium nitride thin film.
The method for manufacturing a gallium nitride thin film according to any one of claims 1 to 3, wherein at least one selected from raw materials containing Sn or Sn is supplied to the surface of the substrate.
、ＺｎまたはＬｉを含む原料から選ばれた少なくとも１
種を基板表面に供給する請求項１〜３のいずれかに記載
の窒化ガリウム薄膜の製造方法。(5) During the production of gallium nitride thin film, Cd, Be, Mg
, at least one selected from raw materials containing Zn or Li
The method for producing a gallium nitride thin film according to any one of claims 1 to 3, wherein seeds are supplied to the surface of the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30039490A JPH04170397A (en) | 1990-11-05 | 1990-11-05 | Production of gallium nitride thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30039490A JPH04170397A (en) | 1990-11-05 | 1990-11-05 | Production of gallium nitride thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04170397A true JPH04170397A (en) | 1992-06-18 |
Family
ID=17884264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30039490A Pending JPH04170397A (en) | 1990-11-05 | 1990-11-05 | Production of gallium nitride thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04170397A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2772187A1 (en) * | 1997-12-09 | 1999-06-11 | Thomson Csf | Producing III-N semiconductor nitride by epitaxial growth in presence of photolytically decomposed ammonia |
| US7456445B2 (en) | 2004-05-24 | 2008-11-25 | Showa Denko K.K. | Group III nitride semiconductor light emitting device |
-
1990
- 1990-11-05 JP JP30039490A patent/JPH04170397A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2772187A1 (en) * | 1997-12-09 | 1999-06-11 | Thomson Csf | Producing III-N semiconductor nitride by epitaxial growth in presence of photolytically decomposed ammonia |
| US7456445B2 (en) | 2004-05-24 | 2008-11-25 | Showa Denko K.K. | Group III nitride semiconductor light emitting device |
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