JPH04342498A - Production of inp single crystal and production of semiconductor device - Google Patents
Production of inp single crystal and production of semiconductor deviceInfo
- Publication number
- JPH04342498A JPH04342498A JP15555391A JP15555391A JPH04342498A JP H04342498 A JPH04342498 A JP H04342498A JP 15555391 A JP15555391 A JP 15555391A JP 15555391 A JP15555391 A JP 15555391A JP H04342498 A JPH04342498 A JP H04342498A
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- concentration
- heat treatment
- cooling
- inp single
- 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.)
- Granted
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000004065 semiconductor Substances 0.000 title claims description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- 238000001816 cooling Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000003708 ampul Substances 0.000 abstract description 3
- 239000010453 quartz Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 230000004913 activation Effects 0.000 description 19
- 235000012431 wafers Nutrition 0.000 description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 238000010583 slow cooling Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000001364 causal effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、Ｐ型ＩｎＰ単結晶の製
造方法に関し、特に高キャリア濃度かつ高活性化率のＺ
ｎドープＩｎＰ単結晶の製造に適用して好適な技術に関
する。[Industrial Application Field] The present invention relates to a method for producing P-type InP single crystals, and in particular to a method for producing P-type InP single crystals, particularly Z-type with high carrier concentration and high activation rate.
The present invention relates to a technique suitable for manufacturing n-doped InP single crystals.
【０００２】0002
【従来の技術】高出力レーザー用基板として使用される
化合物半導体単結晶基板は、低転位密度で高キャリア濃
度であることが要求される。従来、レーザー用基板とし
てはｎ型基板が使われていたが、最近Ｚｎをドープした
Ｐ型ＩｎＰ単結晶基板が用いられるようになった。また
、ＺｎドープＩｎＰ単結晶は原料融液表面をＢ２Ｏ３等
からなる液体封止剤で覆った状態で融液表面に種結晶を
接触させて回転させながら徐々に結晶を引き上げる液体
封止チョクラルスキー法（以下、ＬＥＣ法と称する）に
より製造されていた。2. Description of the Related Art A compound semiconductor single crystal substrate used as a substrate for a high-power laser is required to have a low dislocation density and a high carrier concentration. Conventionally, an n-type substrate has been used as a laser substrate, but recently a P-type InP single crystal substrate doped with Zn has come to be used. In addition, for Zn-doped InP single crystals, the surface of the raw material melt is covered with a liquid sealant made of B2O3, etc., and a seed crystal is brought into contact with the melt surface and the crystal is gradually pulled up while rotating. (hereinafter referred to as the LEC method).
【０００３】しかしながら、上記従来方法にあっては、
原料融液中のＺｎ濃度を高めても育成されたＩｎＰ単結
晶のホール濃度（キャリア濃度）としては７×１０１８
／ｃｍ３が限度で、それ以上のホール濃度（キャリア濃
度）の単結晶を得ることは困難であった。むしろ原料融
液中のＺｎ濃度をある程度以上高めるとホール濃度（キ
ャリア濃度）は低くなるという問題点があった（Ｊｏｕ
ｒｎａｌ ｏｆ Ｃｒｙｓｔａｌ Ｇｒｏｗｔｈ
；６６（１９８４）ｐ３１７−ｐ３２６）。そこで、原
料融液中のＺｎ濃度を７×１０１８−１×１０２０／ｃ
ｍ３としてＬＥＣ法により引き上げた後の単結晶を、そ
のまま炉内において１５０℃／Ｈｒ−９００℃／Ｈｒの
速度で冷却することで、７×１０１８−５×１０１９／
ｃｍ３の高ホール濃度（高キャリア濃度）のＺｎドープ
ＩｎＰ単結晶を製造する方法が提案されている（特開昭
６２−７０２９８号）。However, in the above conventional method,
Even if the Zn concentration in the raw material melt is increased, the hole concentration (carrier concentration) of the grown InP single crystal is 7×1018
/cm3, and it was difficult to obtain a single crystal with a hole concentration (carrier concentration) higher than that. Rather, there was a problem in that when the Zn concentration in the raw material melt was increased beyond a certain level, the hole concentration (carrier concentration) decreased (Jou
rnal of Crystal Growth
;66 (1984) p317-p326). Therefore, the Zn concentration in the raw material melt was set to 7×1018-1×1020/c.
By cooling the single crystal after pulling it by the LEC method as m3 in the furnace at a rate of 150°C/Hr-900°C/Hr, 7×1018-5×1019/
A method for producing a Zn-doped InP single crystal with a high hole concentration (high carrier concentration) of cm3 has been proposed (Japanese Patent Laid-Open No. 70298/1983).
【０００４】0004
【発明が解決しようとする課題】しかしながら、本発明
者らはＺｎドープＩｎＰ単結晶中のＺｎ濃度とホール濃
度（キャリア濃度）との関係について検証した。その結
果、ＬＥＣ法により引き上げた高Ｚｎ濃度の単結晶を、
そのまま炉内において急速冷却しただけではホール濃度
（キャリア濃度）の充分に高いＺｎドープＩｎＰ単結晶
を製造することはできないことが明らかになった。図１
に、ＬＥＣ法により引き上げた後のＺｎドープＩｎＰ単
結晶を、そのまま炉内において炉のヒータ電力を瞬時に
切って急冷した場合（特開昭６２−７０２９８号の方法
）と、炉のヒータ電力を徐々に下げ（１．５ｋｗ／Ｈｒ
）て徐冷（炉冷）した場合の単結晶中のＺｎ濃度とホー
ル濃度（キャリア濃度）の関係を示す。図１に示すよう
に、徐冷するとホール濃度（キャリア濃度）は（３〜４
）×１０１８／ｃｍ３で飽和し（●印）、急冷するとホ
ール濃度（キャリア濃度）は（６〜８）×１０１８／ｃ
ｍ３で飽和した（○印）。However, the present inventors have verified the relationship between Zn concentration and hole concentration (carrier concentration) in a Zn-doped InP single crystal. As a result, a single crystal with a high Zn concentration pulled by the LEC method was
It has become clear that it is not possible to produce a Zn-doped InP single crystal with a sufficiently high hole concentration (carrier concentration) simply by rapidly cooling it in a furnace. Figure 1
In this case, the Zn-doped InP single crystal pulled by the LEC method is immediately cooled in the furnace by immediately turning off the furnace heater power (method of JP-A-62-70298), and the other case when the furnace heater power is turned off immediately. Gradually lower (1.5kw/Hr
) shows the relationship between Zn concentration and hole concentration (carrier concentration) in a single crystal when it is slowly cooled (furnace cooling). As shown in Figure 1, when slowly cooled, the hole concentration (carrier concentration) is (3 to 4
) x 1018/cm3 (● mark), and when rapidly cooled, the hole concentration (carrier concentration) is (6 to 8) x 1018/c
It was saturated with m3 (○ mark).
【０００５】このように、急冷するとホール濃度（キャ
リア濃度）をある程度高くすることはできるものの、ホ
ール濃度（キャリア濃度）／結晶中Ｚｎ濃度を活性化率
と定義したとき、従来の方法にあっては活性化率の高い
結晶が得られないことが明らかになった。As described above, although the hole concentration (carrier concentration) can be increased to some extent by rapid cooling, when the activation rate is defined as the hole concentration (carrier concentration)/Zn concentration in the crystal, the conventional method It became clear that crystals with high activation rate could not be obtained.
【０００６】この発明は上記のような問題点を解決すべ
くなされたもので、その目的とするところは、高ホール
濃度（高キャリア濃度）かつ高活性化率のＺｎドープＩ
ｎＰ単結晶を得ることができる単結晶製造方法を提供す
ることにある。本発明の他の目的は、ＺｎドープＩｎＰ
単結晶を用いた半導体装置の製造工程において行なわれ
る熱処理によりホール濃度（キャリア濃度）が低下され
るのを防止できる半導体装置の製造方法を提供すること
にある。The present invention was made to solve the above-mentioned problems, and its purpose is to provide Zn-doped I with high hole concentration (high carrier concentration) and high activation rate.
An object of the present invention is to provide a single crystal manufacturing method that can obtain an nP single crystal. Another object of the present invention is that Zn-doped InP
An object of the present invention is to provide a method for manufacturing a semiconductor device that can prevent hole concentration (carrier concentration) from being reduced due to heat treatment performed in the manufacturing process of a semiconductor device using a single crystal.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、引上げ炉
から取出した後の単結晶の熱処理の条件の選択によって
、高ホール濃度（高キャリア濃度）かつ高活性化率のＺ
ｎドープＩｎＰ単結晶を得ることができるのではないか
と考え、種々の実験を行なった。その結果、引上げ炉か
ら取り出した後の単結晶を熱処理後に少なくとも４５０
℃から３５０℃までの冷却を３，０００℃／時以上、好
ましくは５，０００℃／時以上の冷却速度で超急冷する
とホール濃度（キャリア濃度）は飽和せず、活性化率を
ほぼ１００％にすることができることを見出した。[Means for Solving the Problems] The present inventors have achieved a high hole concentration (high carrier concentration) and high activation rate Z by selecting the conditions for heat treatment of the single crystal after taking it out from the pulling furnace.
We thought that it might be possible to obtain an n-doped InP single crystal, and conducted various experiments. As a result, the single crystal after being taken out from the pulling furnace has a temperature of at least 450% after heat treatment.
When cooling from ℃ to 350℃ at a cooling rate of 3,000℃/hour or more, preferably 5,000℃/hour or more, the hole concentration (carrier concentration) is not saturated and the activation rate is almost 100%. I found out that it can be done.
【０００８】さらに、本発明者らは、熱処理温度が４０
０℃程度の場合には、熱処理を施した後、超急冷しても
活性化率は上がらないのみならず、熱処理時間が長くな
るに従ってホール濃度（キャリア濃度）はむしろ低下し
てくることを見出した。図２は、ＬＥＣ法によって育成
したＺｎドープＩｎＰ単結晶の基板を４００℃で３時間
熱処理した後、徐冷した場合と超急速冷却した場合の結
晶中のＺｎ濃度とホール濃度（キャリア濃度）との関係
を示す。また、図３には、ＬＥＣ法によって育成したＺ
ｎドープＩｎＰ単結晶を４００℃と３００℃で、３０分
、１時間、３時間それぞれ熱処理した後、急冷した場合
の熱処理時間と結晶中のホール濃度（キャリア濃度）と
の関係が示されている。さらに、図４には、ＬＥＣ法に
よって育成したＺｎドープＩｎＰ単結晶を４００℃と３
５０℃と３００℃で、３時間それぞれ熱処理した後、急
冷した場合の結晶中のホール濃度（キャリア濃度）と熱
処理温度との関係が示されている。Furthermore, the present inventors have determined that the heat treatment temperature is 40
We found that at temperatures around 0°C, not only does the activation rate not increase even when ultra-quenched after heat treatment, but the hole concentration (carrier concentration) actually decreases as the heat treatment time increases. Ta. Figure 2 shows the Zn concentration and hole concentration (carrier concentration) in the crystal when a Zn-doped InP single crystal substrate grown by the LEC method was heat-treated at 400°C for 3 hours and then slowly cooled and ultra-rapidly cooled. shows the relationship between In addition, Fig. 3 shows Z grown by the LEC method.
The relationship between the heat treatment time and the hole concentration (carrier concentration) in the crystal is shown when an n-doped InP single crystal is heat treated at 400°C and 300°C for 30 minutes, 1 hour, and 3 hours, respectively, and then rapidly cooled. . Furthermore, Fig. 4 shows a Zn-doped InP single crystal grown by the LEC method at 400°C and 3°C.
The relationship between the hole concentration (carrier concentration) in the crystal and the heat treatment temperature is shown when the crystal is heat treated at 50° C. and 300° C. for 3 hours and then rapidly cooled.
【０００９】図２より４００℃で熱処理した後、超急速
冷却した場合には、４×１０１８で飽和するものの徐冷
した場合に比べてホール濃度（キャリア濃度）が高くな
ることが分かる。一方、図３より、熱処理温度が３００
℃の場合には熱処理時間の長くなってもホール濃度（キ
ャリア濃度）は変化しないのに、熱処理温度が４００℃
の場合には、熱処理時間が長くなるに従ってホール濃度
（キャリア濃度）はむしろ低下してくることが分かる。
その原因は、４００℃近辺の温度下にＺｎドープＩｎＰ
単結晶を置くと、アクセプタとなるＺｎを補償する何ら
かのドナーとなる欠陥が増加したりあるいはＺｎの析出
物が生じるためと推測される。また、熱処理温度が３５
０℃の場合は４００℃の場合ほど顕著ではないが同じよ
うにホール濃度（キャリア濃度）は低下する。熱処理温
度が３００℃の場合のホール濃度（キャリア濃度）は熱
処理しないもののホール濃度（キャリア濃度）とほぼ同
じ値であり、３００℃の熱処理では活性化率の向上の効
果はないことが分かった。From FIG. 2, it can be seen that when ultra-rapid cooling is performed after heat treatment at 400° C., the hole concentration (carrier concentration) becomes higher than when cooling slowly, although it is saturated at 4×10 18 . On the other hand, from Figure 3, the heat treatment temperature is 300
℃, the hole concentration (carrier concentration) does not change even if the heat treatment time becomes longer, but the heat treatment temperature is 400℃.
In this case, it can be seen that the hole concentration (carrier concentration) actually decreases as the heat treatment time increases. The reason is that Zn-doped InP was produced at a temperature around 400°C.
It is presumed that this is because, when a single crystal is placed, the number of defects that serve as some sort of donor that compensates for Zn, which serves as an acceptor, increases or a precipitate of Zn is generated. In addition, the heat treatment temperature is 35
At 0° C., the hole concentration (carrier concentration) decreases in the same way, although not as markedly as at 400° C. It was found that the hole concentration (carrier concentration) when the heat treatment temperature was 300°C was almost the same as the hole concentration (carrier concentration) without heat treatment, and it was found that heat treatment at 300°C had no effect on improving the activation rate.
【００１０】本発明は、上記知見に基づいてなされたも
ので、Ｚｎを添加したＩｎＰ単結晶を、５００℃−９０
０℃に加熱した後、少なくとも４５０℃から３５０℃ま
での冷却を強制冷却により３，０００℃／Ｈｒ以上、好
ましくは５０００℃／Ｈｒ以上の速度で超急速冷却する
ことにより、例えば高出力レーザーダイオードのような
デバイスの基板となるＺｎドープＩｎＰ単結晶を得るこ
とを提案するものである。上記熱処理される単結晶は、
インゴットのままでもよいが、冷却効率を良くするため
にはブロックもしくはウェーハの状態で行なうのがよい
。また、本発明は、ＺｎドープＩｎＰ単結晶を用いたデ
バイスの製造工程において、行なわれる熱処理の温度条
件を、５００℃以上とし、少なくとも４５０℃から３５
０℃までの冷却を強制冷却により３，０００℃／Ｈｒ以
上の速度で急速冷却することを提案するものである。
ＺｎドープＩｎＰ単結晶を用いたデバイスの製造工程に
おいて行なわれる熱処理としては、例えば金属電極形成
後に良好なオーミック接触を得るために行なう熱処理等
がある。The present invention has been made based on the above findings, and is based on the above findings.
After heating to 0°C, ultra-rapid cooling from at least 450°C to 350°C is performed by forced cooling at a rate of 3,000°C/Hr or more, preferably 5000°C/Hr or more, for example, a high-power laser diode. This paper proposes to obtain a Zn-doped InP single crystal that can serve as a substrate for such devices. The single crystal subjected to the above heat treatment is
Although it may be done as an ingot, it is preferable to use a block or wafer in order to improve the cooling efficiency. Further, in the present invention, in the manufacturing process of a device using a Zn-doped InP single crystal, the temperature condition of the heat treatment performed is 500°C or higher, and at least 450°C to 35°C.
This proposal proposes rapid cooling down to 0°C at a rate of 3,000°C/Hr or more by forced cooling. Heat treatment performed in the manufacturing process of a device using a Zn-doped InP single crystal includes, for example, heat treatment performed after forming a metal electrode in order to obtain good ohmic contact.
【００１１】[0011]
【作用】上記した手段によれば、ＩｎＰ単結晶中のＺｎ
は結晶温度が高いと充分に活性化しているが、冷却する
につれて４００℃付近で活性化率が下がってしまう。し
かるに上記した手段によれば、熱処理後に結晶を超急速
冷却しているため、アクセプタとなるＺｎを補償する何
らかの欠陥が増加する温度帯（４００℃近辺）での熱処
理が回避され、冷却過程でもこの温度帯を素早く通り過
ぎるように急速冷却される。その結果、冷却に伴ってド
ープされたＺｎの活性化率が下がってしまう不具合を防
止し、かつアクセプタとなるＺｎを補償する欠陥あるい
はＺｎの析出物の増加を防止することができる。さらに
、熱処理温度を９００℃以下としたので、ＩｎＰ単結晶
が表面より熱分解するのを防止することができる。[Operation] According to the above-mentioned means, Zn in the InP single crystal
is sufficiently activated when the crystal temperature is high, but as it is cooled, the activation rate decreases around 400°C. However, according to the above-mentioned method, since the crystal is cooled extremely rapidly after heat treatment, heat treatment in the temperature range (near 400°C) where some defects that compensate for Zn, which is an acceptor, increase, is avoided, and even in the cooling process, these defects are avoided. It is rapidly cooled so that it quickly passes through the temperature range. As a result, it is possible to prevent a problem in which the activation rate of doped Zn decreases with cooling, and also to prevent an increase in defects or Zn precipitates that compensate for Zn as an acceptor. Furthermore, since the heat treatment temperature was set to 900° C. or lower, thermal decomposition of the InP single crystal from the surface can be prevented.
【００１２】0012
（実施例１）本発明を適用してＩｎＰ単結晶の製造を行
なった。先ず、るつぼ内にＩｎＰ多結晶を入れかつ融液
中の濃度が３×１０１８−８×１０１８／ｃｍ３となる
量のＺｎを添加して、Ｂ２Ｏ３を封止剤としてＬＥＣ法
によってＺｎドープＩｎＰ単結晶を１０本育成した。引
上げ炉内での冷却は先に述べた徐冷のもの５本と急冷の
もの５本とした。(Example 1) InP single crystal was manufactured by applying the present invention. First, an InP polycrystal is placed in a crucible, Zn is added in an amount such that the concentration in the melt is 3 x 1018-8 x 1018/cm3, and a Zn-doped InP single crystal is formed by the LEC method using B2O3 as a sealant. I grew 10 plants. The cooling in the pulling furnace was performed using the aforementioned five slow cooling methods and five rapid cooling methods.
【００１３】次に、各ＩｎＰ単結晶インゴットをウェー
ハ状に切断した後、各インゴット＃１〜＃１０から隣接
するウェーハを３枚ずつそれぞれ取り出した。そして、
３枚１組のウェーハのうち１枚ずつ計１０枚のウェーハ
は未処理の評価用として残した。また、他の１０枚のウ
ェーハは、６５０℃で０．５ａｔｍの蒸気圧となる量の
赤燐とともに石英アンプル内に真空封入し、上記石英ア
ンプルを加熱炉内に設置して６５０℃に加熱し、３時間
保持した後、水中に入れて強制冷却を行なった。さらに
、残る１０枚のウェーハは、比較のため上記と同一の条
件で熱処理した後に４００℃／Ｈｒの速度で冷却した。
そして、上記３０枚のウェーハについてそれぞれホール
濃度（キャリア濃度）と結晶中Ｚｎ濃度を測定し、その
活性化率を算出した。また、引上げ炉内での冷却条件も
示した。その結果を、表１に示す。Next, after each InP single crystal ingot was cut into wafer shapes, three adjacent wafers were taken out from each ingot #1 to #10. and,
A total of 10 wafers, one wafer in each set of three wafers, were left unprocessed for evaluation. The other 10 wafers were vacuum-sealed in a quartz ampoule with red phosphorus in an amount that would give a vapor pressure of 0.5 atm at 650°C, and the quartz ampoule was placed in a heating furnace and heated to 650°C. After holding the sample for 3 hours, it was placed in water for forced cooling. Furthermore, the remaining 10 wafers were heat treated under the same conditions as above for comparison, and then cooled at a rate of 400° C./Hr. Then, the hole concentration (carrier concentration) and the Zn concentration in the crystal were measured for each of the 30 wafers, and the activation rate was calculated. The cooling conditions within the pulling furnace are also shown. The results are shown in Table 1.
【００１４】[0014]
【表１】
上記表１より、熱処理しなかったウェーハの活性化率は
引上げ炉内で急冷してもＺｎ濃度（６．６〜７．５）×
１０１８／ｃｍ３では８５％−９４％、また冷却速度を
４００℃／Ｈｒ（徐冷）としたときの活性化率はＺｎ濃
度（６．６〜７．５）×１０１８／ｃｍ３では５１％−
６２％であるのに対し、本実施例を適用したものでは活
性化率がすべてのＺｎ濃度で９８％−１０９％とほぼ１
００％になっていることが分かる。[Table 1] From Table 1 above, the activation rate of wafers that were not heat treated was Zn concentration (6.6 to 7.5) x
At 1018/cm3, the activation rate is 85%-94%, and when the cooling rate is 400°C/Hr (slow cooling), the activation rate is 51% at Zn concentration (6.6 to 7.5) x 1018/cm3.
62%, whereas in the case where this example is applied, the activation rate is 98%-109% at all Zn concentrations, which is almost 1.
You can see that it is 00%.
【００１５】図５は、上記測定結果を、横軸にＺｎ濃度
、縦軸にホール濃度（キャリア濃度）をそれぞれとって
プロットしたグラフである。同図において、□印は熱処
理前のもの、○印は６５０℃で３時間熱処理した後徐冷
したもの、＋印は６５０℃で３時間熱処理したのち超急
速冷却したものの測定値を示す。同図より、Ｚｎ濃度が
高くなるほど本発明（熱処理後の超急速冷却）を適用す
ることによって、活性化率が低下するのを有効に防止で
きることが分かる。なお、Ｚｎ濃度は原子吸光法により
、またホール濃度（キャリア濃度）をファン・デル・パ
ウ法により測定した。FIG. 5 is a graph plotting the above measurement results with the horizontal axis representing the Zn concentration and the vertical axis representing the hole concentration (carrier concentration). In the figure, the □ mark indicates the measured value before heat treatment, the ○ mark indicates the measured value after heat treatment at 650°C for 3 hours and then slow cooling, and the + mark indicates the measured value after heat treatment at 650°C for 3 hours and then ultra-rapid cooling. From the figure, it can be seen that the higher the Zn concentration, the more effectively the activation rate can be prevented from decreasing by applying the present invention (ultra-rapid cooling after heat treatment). Note that the Zn concentration was measured by atomic absorption method, and the hole concentration (carrier concentration) was measured by van der Pauw method.
【００１６】上記実施例では強制冷却を水冷にて行なっ
ているが、冷却方法はそれに限定されるものでなく、例
えば熱処理炉内で送風を行なって冷却してもよい。さら
に、上記実施例では結晶をウェーハに切断して熱処理を
行なっているが、数ｃｍ角のブロックあるいは直径が２
インチ以下のような小径の単結晶ではインゴットのまま
熱処理を行なうようにしてもよい。また、熱処理時間は
結晶の大きさや形状等によって最適時間が変わってくる
ので、結晶の大きさや形状に応じて適宜決定してやれば
よい。[0016] In the above embodiment, forced cooling is performed by water cooling, but the cooling method is not limited thereto; for example, cooling may be performed by blowing air inside a heat treatment furnace. Furthermore, in the above embodiment, the crystal is cut into wafers and heat-treated, but the crystal is cut into wafers and the crystal is cut into blocks of several cm square or blocks with a diameter of 2 cm.
Single crystals with a small diameter, such as an inch or less, may be heat treated as an ingot. Further, since the optimum time for heat treatment varies depending on the size and shape of the crystal, it may be determined as appropriate depending on the size and shape of the crystal.
【００１７】（実施例２）るつぼ内にＩｎＰ多結晶を入
れ、かつ融液中の濃度が５×１０１８−９×１０１８／
ｃｍ３となる量のＺｎを添加して、Ｂ２Ｏ３を封止剤と
してＬＥＣ法によって単結晶を引き上げた。次に、各Ｉ
ｎＰ単結晶インゴットをウェーハ状に切断した後、各ウ
ェーハを５つのグループに分け、このうち１つのグルー
プは０．５ａｔｍのリン蒸気圧下で９００℃まで加熱し
１０時間熱処理した後、徐冷した。他の２つは０．５ａ
ｔｍのリン蒸気圧下で５００℃まで加熱し、それぞれ１
０時間熱処理したのち徐冷および３時間熱処理したのち
急冷した。また、残りのうち１つは０．００５ａｔｍの
リン蒸気圧下で６５０℃まで加熱し３時間熱処理したの
ち徐冷し、他の１つは熱処理せず評価用とした。(Example 2) InP polycrystals were placed in a crucible, and the concentration in the melt was 5×10 18 -9×10 18 /
cm3 of Zn was added, and the single crystal was pulled by the LEC method using B2O3 as a sealant. Next, each I
After cutting the nP single crystal ingot into wafer shapes, each wafer was divided into five groups, one group of which was heated to 900° C. under a phosphorous vapor pressure of 0.5 atm, heat-treated for 10 hours, and then slowly cooled. The other two are 0.5a
Heating to 500°C under phosphorus vapor pressure of tm, each
After heat treatment for 0 hours, it was slowly cooled, and after heat treatment for 3 hours, it was rapidly cooled. In addition, one of the remaining samples was heated to 650° C. under a phosphorus vapor pressure of 0.005 atm, heat-treated for 3 hours, and then slowly cooled, and the other one was used for evaluation without heat treatment.
【００１８】図６は、上記各ウェーハのＺｎ濃度および
ホール濃度（キャリア濃度）を測定した結果を、横軸に
Ｚｎ濃度、縦軸にホール濃度（キャリア濃度）をそれぞ
れとってプロットしたグラフである。同図において、○
印は熱処理前のもの、△印は９００℃で１０時間熱処理
したのち徐冷したもの、●印は５００℃で１０時間熱処
理したのち徐冷したもの、■印は６５０℃で３時間熱処
理したのち急冷したもの、□印は０．００５ａｔｍのリ
ン蒸気圧下で６５０℃まで加熱し３時間熱処理したのち
徐冷したものの測定値を示す。FIG. 6 is a graph plotting the results of measuring the Zn concentration and hole concentration (carrier concentration) of each of the wafers, with the horizontal axis representing the Zn concentration and the vertical axis representing the hole concentration (carrier concentration). . In the same figure, ○
The mark is before heat treatment, the △ mark is after heat treatment at 900℃ for 10 hours and then slow cooling, the ● mark is after heat treatment at 500℃ for 10 hours and then slow cooling, the ■ mark is after heat treatment at 650℃ for 3 hours. The □ mark indicates the measured value of the sample that was heated to 650° C. under a phosphorus vapor pressure of 0.005 atm, heat-treated for 3 hours, and then slowly cooled.
【００１９】同図より、５００℃においても、徐冷する
よりも急冷したほうがホール濃度（キャリア濃度）が高
くなることが分かる。従って、熱処理後に超急速冷却を
おこなうことによりさらにホール濃度（キャリア濃度）
を高め、Ｚｎ濃度の高い領域で活性化率が低下するのを
防止できると推定される。また、図６における□印（０
．００５ａｔｍのリン蒸気圧下で６５０℃まで加熱し３
時間熱処理した後、徐冷したものの測定値）と、図５に
おける○印（０．５ａｔｍのリン蒸気圧下で６５０℃で
３時間熱処理した後徐冷したものの測定値）とを比較す
ると分かるように、ホール濃度（キャリア濃度）とリン
蒸気圧との因果関係はあまり見られない。熱処理雰囲気
はリン蒸気圧下に限らず、Ｎ２雰囲気や真空中でも同様
の効果が得られる。From the figure, it can be seen that even at 500° C., the hole concentration (carrier concentration) is higher when rapidly cooled than when slowly cooled. Therefore, by performing ultra-rapid cooling after heat treatment, the hole concentration (carrier concentration) can be further reduced.
It is estimated that this can increase the Zn concentration and prevent the activation rate from decreasing in regions with high Zn concentrations. In addition, the □ mark (0
．． Heating to 650°C under phosphorus vapor pressure of 0.005 atm 3
As can be seen by comparing the measured value of the product after heat treatment for 3 hours and then slow cooling) with the circle mark in Figure 5 (measured value of the product after heat treatment at 650 ° C. for 3 hours under 0.5 atm phosphorus vapor pressure and then slow cooling). , there is not much of a causal relationship between hole concentration (carrier concentration) and phosphorus vapor pressure. The heat treatment atmosphere is not limited to phosphorus vapor pressure, but similar effects can be obtained even in N2 atmosphere or vacuum.
【００２０】[0020]
【発明の効果】以上説明したように、本発明にあっては
、Ｚｎを添加したＩｎＰ単結晶を５００℃−９００℃に
加熱した後、少なくとも４５０℃から３５０℃までの冷
却を強制冷却により３０００℃／Ｈｒ以上、好ましくは
５０００℃／Ｈｒ以上の速度で急速冷却するようにした
ので、アクセプタとなるＺｎを補償する何らかの欠陥が
増加する温度帯（４００℃近辺）での熱処理が回避され
、冷却過程でもこの温度帯を素早く通り過ぎてしまうた
め、冷却に伴ってドープされたＺｎの活性化率が下がっ
てしまう不具合が防止され、かつアクセプタとなるＺｎ
を補償する欠陥あるいはＺｎの析出物の増加を防止され
、高ホール濃度（高キャリア濃度）かつ高活性化率のＺ
ｎドープＩｎＰ単結晶が得られるようになるという効果
がある。また、ＺｎドープＩｎＰ単結晶を用いた半導体
装置の製造工程において行なわれる熱処理を、５００℃
以上の温度にて行なった後、少なくとも４５０℃から３
５０℃までの冷却を強制冷却により３０００℃／Ｈｒ以
上の速度で急速冷却するようにしたので、熱処理により
基板表面の活性領域のホール濃度（キャリア濃度）が低
下されるのを防止できるという効果がある。As explained above, in the present invention, after heating an InP single crystal doped with Zn to 500°C to 900°C, cooling from at least 450°C to 350°C is performed by forced cooling for 3000°C. Since rapid cooling is performed at a rate of ℃/Hr or more, preferably 5000℃/Hr or more, heat treatment in the temperature range (near 400℃) where some defects that compensate for the acceptor Zn increase is avoided, and cooling Since the process quickly passes through this temperature range, the problem that the activation rate of doped Zn decreases with cooling is prevented, and the Zn that becomes an acceptor
Zn with high hole concentration (high carrier concentration) and high activation rate is prevented from increasing defects or Zn precipitates to compensate for
This has the effect that an n-doped InP single crystal can be obtained. In addition, the heat treatment performed in the manufacturing process of semiconductor devices using Zn-doped InP single crystal is heated to 500°C.
After carrying out at a temperature of at least 450°C
Since cooling down to 50°C is rapidly cooled at a rate of 3000°C/Hr or more by forced cooling, it is possible to prevent the hole concentration (carrier concentration) in the active region of the substrate surface from decreasing due to heat treatment. be.
【図１】従来のＺｎドープＩｎＰ単結晶の製造方法にお
ける融液中Ｚｎ濃度とホール濃度（キャリア濃度）との
関係を示すグラフである。FIG. 1 is a graph showing the relationship between the Zn concentration in the melt and the hole concentration (carrier concentration) in a conventional method for manufacturing a Zn-doped InP single crystal.
【図２】ＬＥＣ法によって育成したＺｎドープＩｎＰ単
結晶の基板を４００℃で３時間熱処理した後、徐冷した
場合と超急速冷却した場合の結晶中のＺｎ濃度とホール
濃度（キャリア濃度）との関係を示すグラフである。[Figure 2] Zn concentration and hole concentration (carrier concentration) in the crystal when a Zn-doped InP single crystal substrate grown by the LEC method was heat-treated at 400°C for 3 hours and then slowly cooled and ultra-rapidly cooled. It is a graph showing the relationship.
【図３】ＬＥＣ法によって育成したＺｎドープＩｎＰ単
結晶を４００℃と３００℃で、３０分、１時間、３時間
それぞれ熱処理した後、徐冷した場合の熱処理時間と結
晶中のホール濃度（キャリア濃度）との関係を示すグラ
フである。[Fig. 3] Heat treatment time and hole concentration (carrier FIG.
【図４】ＬＥＣ法によって育成したＺｎドープＩｎＰ単
結晶を４００℃と３５０℃と３００℃で、３時間それぞ
れ熱処理した後、徐冷した場合の結晶中のホール濃度（
キャリア濃度）と熱処理温度との関係を示すグラフであ
る。FIG. 4: Hole concentration in the crystal (
2 is a graph showing the relationship between carrier concentration) and heat treatment temperature.
【図５】本発明の第１の実施例を適用して得られたＺｎ
ドープＩｎＰ単結晶と従来の熱処理方法により得られた
ＺｎドープＩｎＰ単結晶および熱処理前のＺｎドープＩ
ｎＰ単結晶のＺｎ濃度とホール濃度（キャリア濃度）と
の関係を示すグラフである。FIG. 5: Zn obtained by applying the first example of the present invention
Doped InP single crystal, Zn-doped InP single crystal obtained by conventional heat treatment method, and Zn-doped I before heat treatment
2 is a graph showing the relationship between Zn concentration and hole concentration (carrier concentration) of an nP single crystal.
【図６】従来の熱処理方法により得られたＺｎドープＩ
ｎＰ単結晶および熱処理前のＺｎドープＩｎＰ単結晶の
Ｚｎ濃度とホール濃度（キャリア濃度）との関係を示す
グラフである。[Fig. 6] Zn-doped I obtained by conventional heat treatment method
2 is a graph showing the relationship between Zn concentration and hole concentration (carrier concentration) in an nP single crystal and a Zn-doped InP single crystal before heat treatment.
Claims (2)
を、５００℃−９００℃に加熱した後、少なくとも４５
０℃から３５０℃までの冷却を強制冷却により３０００
℃／Ｈｒ以上の速度で急速冷却するようにしたことを特
徴とするＩｎＰ単結晶の製造方法。Claim 1: After heating an InP single crystal to which Zn (zinc) has been added to 500°C to 900°C,
Cooling from 0℃ to 350℃ by forced cooling
A method for producing an InP single crystal, characterized in that rapid cooling is performed at a rate of at least ℃/Hr.
半導体装置の製造工程において行なわれる熱処理を、５
００℃以上の温度にて行なった後、少なくとも４５０℃
から３５０℃までの冷却を強制冷却により３０００℃／
Ｈｒ以上の速度で急速冷却するようにしたことを特徴と
する半導体装置の製造方法。2. Heat treatment performed in the manufacturing process of a semiconductor device using a Zn-doped InP single crystal as a substrate is
At least 450℃ after carrying out at a temperature of 00℃ or higher
Cooling from 350℃ to 3000℃/300℃ by forced cooling
A method for manufacturing a semiconductor device, characterized in that rapid cooling is performed at a rate of Hr or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15555391A JPH0798720B2 (en) | 1990-10-23 | 1991-05-31 | InP single crystal manufacturing method and semiconductor device manufacturing method |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-285478 | 1990-10-23 | ||
| JP28547890 | 1990-10-23 | ||
| JP15555391A JPH0798720B2 (en) | 1990-10-23 | 1991-05-31 | InP single crystal manufacturing method and semiconductor device manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04342498A true JPH04342498A (en) | 1992-11-27 |
| JPH0798720B2 JPH0798720B2 (en) | 1995-10-25 |
Family
ID=26483518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15555391A Expired - Lifetime JPH0798720B2 (en) | 1990-10-23 | 1991-05-31 | InP single crystal manufacturing method and semiconductor device manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0798720B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018179567A1 (en) * | 2017-03-31 | 2018-10-04 | Ｊｘ金属株式会社 | Compound semiconductor and method for producing single crystal of compound semiconductor |
-
1991
- 1991-05-31 JP JP15555391A patent/JPH0798720B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018179567A1 (en) * | 2017-03-31 | 2018-10-04 | Ｊｘ金属株式会社 | Compound semiconductor and method for producing single crystal of compound semiconductor |
| KR20190043626A (en) * | 2017-03-31 | 2019-04-26 | 제이엑스금속주식회사 | Compound semiconductor and method for manufacturing compound semiconductor single crystal |
| CN109963967A (en) * | 2017-03-31 | 2019-07-02 | Ｊｘ金属株式会社 | The manufacturing method of compound semiconductor and compound semiconductor single crystal |
| JPWO2018179567A1 (en) * | 2017-03-31 | 2020-02-13 | Ｊｘ金属株式会社 | Method for producing compound semiconductor and compound semiconductor single crystal |
| TWI699464B (en) * | 2017-03-31 | 2020-07-21 | 日商Ｊｘ金屬股份有限公司 | Compound semiconductor and compound semiconductor single crystal manufacturing method |
| EP3591102A4 (en) * | 2017-03-31 | 2021-01-06 | JX Nippon Mining & Metals Corporation | Compound semiconductor and method for producing single crystal of compound semiconductor |
| CN109963967B (en) * | 2017-03-31 | 2021-07-20 | Ｊｘ金属株式会社 | Compound semiconductor and method for producing compound semiconductor single crystal |
| US11371164B2 (en) | 2017-03-31 | 2022-06-28 | Jx Nippon Mining & Metals Corporation | Compound semiconductor and method for producing single crystal of compound semiconductor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798720B2 (en) | 1995-10-25 |
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