JP2002217122A - Method for depositing nitrogen-containing compound semiconductor and method for depositing niride-based group iii-v compound semiconductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily depositing a compound semiconductor containing nitrogen of good crystallinity or a semiconductor of a nitride-based group III-V compound. SOLUTION: When a compound semiconductor containing nitrogen or a semiconductor of a nitride-based group III-V compound is deposited by a vapor deposition method, e.g. an organic metal chemical vapor deposition method, an organic compound which contains at least one nitrogen atom and at least two groups of which a molar weight is at least larger than 36 is bonded to the nitrogen atom, e.g. a diisopropylamine is used as a nitrogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for growing a compound semiconductor containing nitrogen and a method for growing a nitride III-V compound semiconductor.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for a semiconductor laser capable of emitting light at a short wavelength in order to improve the recording density of an optical disc and the resolution of a laser printer. It is being actively conducted.

As a material used for manufacturing a semiconductor laser capable of emitting light at such a short wavelength, a II-VI group compound semiconductor is promising. In particular, a ZnMgSSe-based compound semiconductor, which is a quaternary II-VI compound semiconductor,
It is known that it is suitable for a material of a cladding layer or an optical waveguide layer when a blue or green light emitting semiconductor laser having a wavelength of 400 to 550 nm is formed on a GaAs substrate (for example, Electron. Lett. 28, 1798). (1992)).

Heretofore, II-VI compound semiconductors have been grown exclusively by molecular beam epitaxy (MBE), but this MBE is not satisfactory in terms of productivity. Therefore, in recent years, attempts have been made to apply a metal organic chemical vapor deposition (MOCVD) method, which has excellent productivity and is widely used as a method for growing a group III-V compound semiconductor, to the growth of a group II-VI compound semiconductor. .

On the other hand, nitrogen (N) has been most often used as an acceptor impurity for obtaining a p-type II-VI group compound semiconductor such as p-type ZnSe.
When growing the p-type II-VI compound semiconductor by MOCVD, ammonia (NH ₃ ), tertiary butylamine (t-BNH ₂ ), and hydrazine (N ₂ H ₄ ) are used as p-type dopants. ) Are commonly used.

[0006]

However, when NH ₃ , t-BNH ₂ , N ₂ H ₄ or the like is used as a p-type dopant as described above, the doping efficiency of N is extremely low, and the supply of N Unless the amount is considerably increased, there is a problem that N is not doped. For example, it has been reported that when NH ₃ is used as a p-type dopant, clear N doping does not occur unless it is supplied at several thousand μmol / min (for example, J. Crystal Growth 10).
1, 305 (1990) and J. Crystal Growth 99, 413 (199
0)). For this reason, p-type I-type semiconductors having a sufficiently high N doping concentration, that is, an acceptor concentration, have hitherto been used.
It has been difficult to grow I-VI group compound semiconductors. Specifically, for example, in the case of p-type ZnSe, the acceptor concentration is 1 × 10 ¹⁶ cm ⁻³ even if all means are exhausted.
Was the limit.

[0007] One of the reasons why the N doping efficiency is low as described above is that N is hardly taken into the grown crystal. The reason for this is that the vapor pressure of nitrogen molecules (N ₂ ) at the growth temperature is very high, and even if an attempt is made to dope N, most of the N is desorbed as N ₂ during migration on the surface of the grown crystal. Can be considered. The fact that the vapor pressure of N _{2 at} the growth temperature is actually very high can be seen from the following. That is, the vapor pressure of N ₂ can be expressed by the following equation called the Antoine equation log (p / mmHg) = 6.449594−255.821 / (266.56+ (T / ° C.)) (for example, Chemical Handbook, Basic Edition II).
(Edited by the Chemical Society of Japan)), this formula indicates that N _{2 at} 500 ° C., which is the general growth temperature of II-VI group compound semiconductors,
Has a vapor pressure of 1.45 × 10 ⁶ Torr and a normal pressure (1
1860 times higher than atmospheric pressure).

As a method for solving the above-mentioned problem of desorption of N, II-VI by molecular beam epitaxy (MBE) is used.
There are plasma doping method which is often used in the family compound semiconductor growth, which is the atom of the crystal surface (main by doping with an N ₂ plasma form I
It is considered that the desorption of N is prevented by inducing a bond with a group I element atom). However, it is difficult to use this plasma doping method for growing a II-VI compound semiconductor by MOCVD because the pressure is too high. That is, the pressure in the reaction tube when growing by MOCVD is limited to normal pressure to several Torr even if the pressure is reduced. However, at such a high pressure, the life of the plasma is extremely short, and the plasma becomes short before reaching the substrate surface. Because it is gone.

As described above, it has been difficult to grow a p-type II-VI group compound semiconductor having a sufficiently high acceptor concentration. However, this is because a semiconductor laser using a II-VI group compound semiconductor is used. It is a major obstacle in the manufacture of light-emitting elements such as light-emitting diodes and light-emitting diodes.

Accordingly, an object of the present invention is to provide a p-type II-VI compound semiconductor capable of growing a p-type II-VI compound semiconductor having a sufficiently high acceptor concentration, that is, a doping concentration of nitrogen as an acceptor impurity. It is to provide a growth method. On the other hand, a compound semiconductor containing nitrogen, when growing such as such as GaN by MOCVD, As the nitrogen source is generally used NH _3, and suppressing the loss of nitrogen in the grown crystal, the crystallinity degradation To prevent this, it was necessary to make the NH ₃ flow rate during growth extremely large. Therefore, an object of the present invention is to provide a method for growing a compound semiconductor containing nitrogen, which can easily grow a compound semiconductor containing nitrogen with good crystallinity, and a nitride III-V compound semiconductor with good crystallinity. Nitride III- which can be easily grown
An object of the present invention is to provide a method for growing a group V compound semiconductor.

[0011]

According to the present invention, there is provided an organic compound comprising at least one nitrogen atom having at least two groups having a molecular weight greater than at least 36 bonded to the nitrogen atom. A method for growing a compound semiconductor containing nitrogen, wherein a compound semiconductor containing nitrogen is grown by a vapor phase growth method using a compound as a nitrogen source. The present invention also provides a method for producing a nitride-based compound using an organic compound containing at least one nitrogen atom and having at least two groups having a molecular weight greater than at least 36 bonded to the nitrogen atom as a nitrogen source.
A method for growing a nitride-based III-V compound semiconductor, characterized in that a -V compound semiconductor is grown by a vapor phase growth method.

In the present invention, the molecular weight of at least two groups bonded to a nitrogen atom in an organic compound as a nitrogen source is such that these groups are easily thermally decomposed even at a temperature of about 500 ° C. to be liberated from the nitrogen atom. To make sure
As described above, it is selected to be larger than 36. Further, in order that these groups are thermally decomposed and liberated from a nitrogen atom with an equal probability, those having the same molecular weight are preferably used as these groups.

In the present invention, the organic compound as a nitrogen source typically contains one nitrogen atom, and two hydrogen groups having a molecular weight greater than 36 and one hydrogen atom are bonded to the nitrogen atom. Organic compounds containing one nitrogen atom, and three groups having a molecular weight greater than 36 bonded to the nitrogen atom. Examples of the former organic compound include the following (a) to (f), and examples of the latter organic compound include the following (g) to (r).

(A) Diisopropylamine (Di-PN
H)

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(B) Dipropylamine (D-PNH)

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(C) dibutylamine (D-BNH)

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(D) Diisobutylamine (Di-BN)
H)

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(E) Disecondary butylamine (Ds-BN)
H)

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(F) Ditertiary butylamine (Dt-
BNH)

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(G) Tripropylamine (T-PN)

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(H) Triisopropylamine (Ti-P
N)

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(I) Tributylamine (T-BN)

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(J) Triisobutylamine (Ti-B
N)

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(K) Trisecondary butylamine (Ts-B
N)

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(L) Tritert-butylamine (Tt)
-BN)

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(M) Diisopropylmethylamine (Di)
-PMN)

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(N) Dipropylmethylamine (D-PM
N)

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(O) Dibutylmethylamine (D-BM
N)

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(P) Diisobutylmethylamine (Di-
BMN)

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(Q) Disecondary butylmethylamine (Ds-
BMN)

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(R) Ditert-butyl methylamine (Dt-BMN)

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The following organic compounds (a) to (r) are conventionally used as a nitrogen source. The following ammonia (NH ₃ ) and tertiary butylamine (t-BNH ₂ )
As is apparent from comparison with, in NH ₃ and t-BNH ₂ , one or less groups are bonded to the N atom, and the number of H atoms directly bonded to the N atom is two or three. On the other hand, in the organic compounds (a) to (r),
Two or three groups are bonded to the N atom, and the number of H atoms directly bonded to the N atom is one or less.

(S) Ammonia (NH ₃ )

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(T) Tertiary butylamine (t-BN)
H ₂ )

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In a preferred embodiment of the present invention,
A nitrogen atom is delta-doped (δ-doped) on the surface of the group II element of the II-VI compound semiconductor. Further, instead of the delta doping, a flow modulation method capable of obtaining the same effect as the delta doping may be used. Specifically, in this flow modulation method, the supply of the group II element source and the supply of the p-type dopant are maintained, and the supply of the group VI element source is interrupted to interrupt the growth.

In the present invention, the vapor phase growth method includes
In addition to the MOCVD method, an MBE method using a gas source can be used.

In the present invention, the grown II
The group VI compound semiconductor is, for example, Zn _1-ab Mg _a Cd
_{b S c Te d Se 1-} cd -based compound semiconductor (where, 0 ≦
a, b, c, d <1), and more specifically, ZnS
e, ZnSSe, ZnCdSe, ZnMgSSe, and the like.

[0038]

According to the present invention constructed as described above,
According to the method of growing a Group VI compound semiconductor, the p-type dopant is composed of an organic compound in which at least one nitrogen atom is bonded and at least two groups having a molecular weight of at least greater than 12 are bonded to the nitrogen atom. After these groups are thermally decomposed and released from the nitrogen atom, the nitrogen atom has at least two bonds (dangling bonds), and NH ₃ , t-BNH _2, or the like is replaced with a p-type dopant as in the prior art. The number of bonds of nitrogen atoms after thermal decomposition is at least one larger than that in the case of using the compound as above. For this reason, the nitrogen atoms are more likely to be combined with atoms on the surface of the grown crystal and taken in by that amount, so that the efficiency of doping the grown II-VI compound semiconductor with nitrogen atoms can be increased. As a result, a doping concentration of nitrogen atoms as acceptor impurities, that is, a II-VI group compound semiconductor having a sufficiently high acceptor concentration can be grown.

In particular, when an organic compound containing one nitrogen atom and having three nitrogen atoms having a molecular weight greater than 36 bonded to the nitrogen atom is used as a p-type dopant, hydrogen is added to the nitrogen atom. Due to the fact that the atoms are not directly bonded, the nitrogen atoms are formed independently after pyrolysis, rather than in a form bonded to hydrogen atoms. Therefore, when an organic compound is used as a p-type dopant, hydrogen atoms contained in the p-type dopant are incorporated into the grown crystal, and the hydrogen atoms inactivate nitrogen atoms as acceptor impurities, that is, Problems of passivation of nitrogen atoms by hydrogen atoms (for example, Appl. Phys. Lett. 62, 270 (199
1)) can also be solved. As a result, it is possible to grow a II-VI group compound semiconductor having a higher acceptor concentration.

Further, the II-VI compound semiconductor II
By delta doping nitrogen atoms on the surface of group element,
Alternatively, by using a flow modulation method, the efficiency of incorporation of nitrogen atoms into the grown crystal can be further increased, whereby a p-type II-VI group compound semiconductor having a higher acceptor concentration can be grown. it can.

[0041]

Embodiments of the present invention will be described below with reference to the drawings. First, an MOCVD apparatus used in the first embodiment of the present invention will be described. FIG. 1 shows the configuration of the MOCVD apparatus.

As shown in FIG. 1, in this MOCVD apparatus, hydrogen (H ₂ ) gas highly purified by the H ₂ purifying apparatus 1 is supplied into the bubblers 2, 3, and 4 as a carrier gas. Now, considering the case where p-type ZnSe is grown, for example, dimethyl zinc (DMZ) as a Zn raw material is provided in these bubblers 2, 3, and 4, respectively.
n), dimethyl selenium (DMSe) as a Se raw material, and Di-PNH as a p-type dopant. By supplying H ₂ gas into these bubblers 2, 3, and 4, the raw material gas corresponding to the vapor pressure from each of these bubblers 2, 3, and 4 reacts with H ₂ gas as a carrier gas. It is supplied into the reaction tube 6 through the tube line 5. A susceptor 7 is installed in the reaction tube 6,
The substrate 8 is placed thereon.

Reference numeral 9 denotes a vent line. in this case,
Switching of the source gas generated from the bubbler 2 between the reaction tube line 5 and the vent line 9 can be performed by opening and closing the valves V ₁ and V _2. Switching between the valve 5 and the vent line 9 can be performed by opening and closing the valves V ₃ and V _4. Switching of the dopant gas generated from the bubbler 4 between the reaction tube line 5 and the vent line 9 is performed. Valve V
_5, and it is capable of performing the opening and closing of V _6. Reference numerals 10 to 14 denote mass flow controllers for controlling the flow rate of the H ₂ gas supplied from the H ₂ purifying apparatus 1.

FIG. 2 shows a p-type Z according to the first embodiment of the present invention.
FIG. 4 is a sequence diagram showing a state of supply of a source gas and a dopant gas in an nSe growth method. In the first embodiment, first, a semi-insulating Ga is formed as a substrate 8 on a susceptor 7 in a reaction tube 6 of the MOCVD apparatus shown in FIG.
The As substrate 21 (FIG. 3) is placed, and the semi-insulating GaAs substrate 21 is heated by the susceptor 7 to a growth temperature in an H ₂ gas atmosphere.

Next, DM as a Zn raw material is placed in the reaction tube 6.
All of Zn, DMSe as a Se raw material and Di-PNH as a p-type dopant are simultaneously supplied (FIG. 2). As a result, as shown in FIG.
On an As substrate 21, an N-doped ZnSe layer (in this first embodiment and the next second embodiment, “ZnSe:
22) is epitaxially grown.

FIG. 4 shows the result of measuring the photoluminescence spectrum of the ZnSe: N layer 22 epitaxially grown as described above at 4.2 K (liquid helium temperature). However, the growth temperature is 450 ° C., and the pressure in the reaction tube 6 is 650 Torr. In addition, DMZn, DM
The supply amounts of Se and Di-PNH were 5 μmo, respectively.
1 / min, 10 μmol / min and 141 μmol / min.

On the other hand, for comparison, as in the conventional epitaxial growth method by the MOCVD method, DMZn as a Zn raw material and DMSe as a Se raw material are placed in the reaction tube 6.
And a sample in which a ZnSe: N layer is epitaxially grown on a semi-insulating GaAs substrate by simultaneously supplying all of t-BNH ₂ as a p-type dopant,
e: Photoluminescence spectrum of N layer is 4.2K
Was measured. The result is shown in FIG. However, the growth temperature is 450 ° C., and the pressure in the reaction tube 6 is 650 Torr. The supply amounts of DMZn, DMSe and t-BNH ₂ are 5 μmol / min, 10 μmol / min and 180 μmol / min, respectively. 4 and 5
Note that the full scales of the vertical axes of are different from each other.

The most different point between FIG. 4 and FIG. 5 is that
This is the presence / absence of DAP (donor-acceptor pair) emission observed near a wavelength of 460 nm. That is, while strong DAP emission is observed in FIG.
AP emission is hardly observed. This DAP emission is evidence that N is doped, and the higher the intensity, the greater the N doping amount. 4 and 5, the ZnSe: N layer 22 grown by the growth method according to the first embodiment is different from the ZnSe: N layer grown by the conventional MOCVD method using t-BNH ₂ as a p-type dopant. Unlikely, it is considered that a large amount of N is doped.

In FIGS. 4 and 5, the peak other than the DAP emission is I ₁ (neutral acceptor-bound exciton).
Light emission, phonon replica of DAP light emission, and Y light emission (light emission due to misfit dislocation).

The N-doped amount of the ZnSe: N layer 22 grown by the growth method according to the first embodiment is determined by the capacitance (C).
As shown in FIGS. 6 and 7, a semi-insulating GaAs substrate 21 is used for quantitative evaluation by a voltage (V) measuring method.
1.3 μm thick ZnS epitaxially grown on
e: samples were produced formed a circular gold (Au) electrodes E ₁ and Au electrode E ₂ around it by N layer vacuum deposition method on 22. Here, the area around the Au electrode E _2, by sufficiently larger than the area of the circular Au electrode E _1,
The surrounding Au electrode E ₂ can be approximately regarded as an ohmic electrode. In this case, the diameter of the circular Au electrode E ₁ is 336 μm.

In the samples shown in FIGS. 6 and 7,
A negative bias voltage and a positive bias voltage were applied to the circular Au electrode E ₁ and the surrounding Au electrode E ₂ , respectively, to perform CV measurement. FIG. 8 shows the result. FIG.
As can be seen from FIG. 6, the capacitance (C) tends to decrease as the negative bias voltage increases. Furthermore, Z
Assuming that the relative dielectric constant of nSe is 9.3, the ZnSe: N layer 22
Effective acceptor concentration in the depth direction from the surface of the (N _A -N _D
(N _A: acceptor concentration, N _D: donor concentration)) was estimated, the results shown in FIG. 9 was obtained. Then, when N _A −N _D was obtained from this result, N _A −N
_{D was} 2 × 10 ¹⁶ cm ⁻³ . This level of acceptor concentration is sufficient for fabricating a light emitting device such as a semiconductor laser, which indicates that Di-PNH is effective as a p-type dopant in growing a II-VI group compound semiconductor by MOCVD. I understand.

The approximate value of the doping amount of N in the ZnSe: N layer 22 can be estimated as follows without actually performing the CV measurement as described above. That is, generally, there is a close relationship between the intensity of DAP emission and the acceptor concentration, and as the acceptor concentration increases, the relative intensity of DAP emission increases. FIG. 10 shows the low-temperature photoluminescence spectrum and secondary ion mass spectrometry (SIM) reported by J. Qiu et al.
S) N concentration ([N]) and CV measured by the method
Effective acceptor concentration (N _A -N
_D ) (Appl. Phys. Lett. 59, 2992 (199)
1)). Similar results have been reported by Z. Yang et al. (Appl. Phys. Lett. 61, 2671 (1992)). Figure 1
From 0, the acceptor concentration of the ZnSe: N layer 22 grown by the growth method according to the first embodiment is 1.0 × 10 ¹⁶ cm ^{−3 as the} effective acceptor concentration according to the CV measurement method.
It can be estimated that it is in the range of <N _A −N _D <8.0 × 10 ¹⁷ cm ⁻³ .

As described above, according to the growth method according to the first embodiment, the use of Di-PNH as the p-type dopant makes it possible to use ZnS doped with a high concentration of N.
e: N layer 24, that is, p-type Zn having a high acceptor concentration
The Se layer can be grown. The reason that the p-type ZnSe layer having a high acceptor concentration can be grown as described above is that the N-atom generated by the thermal decomposition of Di-PNH has two bonds in the growth, which makes it possible to grow the ZnSe crystal. This is because the incorporation efficiency of N is high, and thus the doping efficiency of N is high.

Next, a second embodiment of the present invention will be described. In the second embodiment, N is doped by a flow modulation method capable of obtaining substantially the same effect as δ doping.

FIG. 11 is a sequence diagram showing a supply state of a source gas and a dopant gas in the p-type ZnSe growth method according to the second embodiment of the present invention. 12A to 12E show t = t ₁ , t ₂ , t ₃ , and t = t ₁ in FIG.
The state of the grown layer at each time point of t ₄ and t ₅ is shown.

Hereinafter, a method for growing p-type ZnSe according to the second embodiment will be described with reference to FIGS. 1, 11, and 12. First, a semi-insulating GaAs substrate 2 as a substrate 8 is placed on a susceptor 7 in a reaction tube 6 of the MOCVD apparatus shown in FIG.
1, and the GaAs substrate 21 is heated by the susceptor 7 to a growth temperature in an H ₂ gas atmosphere.

Next, DM as a Zn raw material is placed in the reaction tube 6.
By simultaneously supplying all of Zn, DMSe as a raw material of Se, and Di-PNH as a p-type dopant, as shown in FIG.
A ZnSe: N layer 23 is epitaxially grown thereon.
This epitaxial growth of the ZnSe: N layer 23 is performed from time t = 0 to time t = t ₁ (FIG. 12). The ZnSe: N layer 23 that is first epitaxially grown becomes a buffer layer of the ZnSe: N layer that is subsequently grown.

Next, at time t = t _1, to interrupt the supply of DMSe while maintaining the supply of DMZn and Di-PNH, performing growth interruption. This growth interruption occurs at time t =
performed until t _2. During this growth interruption, Zn is adsorbed on the surface of the ZnSe: N layer 23 as a buffer layer due to the thermal decomposition of DMZn supplied into the reaction tube 6, and the surface is covered with the Zn adsorption layer. Zn in Zn adsorption layer
Then, N having two bonds generated by the thermal decomposition of Di-PNH is adsorbed, whereby N is taken into the growth layer. In FIG. 12B, the adsorption layer of Zn and N is indicated by reference numeral 24.

FIG. 13A shows a state in which N atoms having two bonds generated by thermal decomposition of Di-PNH are bonded to the surface of Zn which is a group II element of the ZnSe crystal. As shown in FIG. 13A, in this case, N atoms are bonded by two bonds across two Zn atoms on the surface of Zn, so that the bonding force between Zn atoms and N atoms is strong, Desorption of the N atom is unlikely to occur. In addition, N atoms are bonded by directly reflecting the crystal structure of ZnSe. on the other hand,
When t-BNH ₂ is used as a p-type dopant,
Since the N atom generated by the thermal decomposition of t-BNH ₂ has only one bond, as shown in FIG. 13B, two N atoms each correspond to one Zn atom on the Zn surface. To join with the joint. In this case, N is easily desorbed due to a weak bonding force with Zn atoms, and extra N is also present.

Next, at time t = t ₂ , the supply of DMSe into the reaction tube 6 is restarted, and this DSe is supplied until time t = t _3.
Continue to supply MSe. As a result, DMZn, DMSe and Di-PNH are all simultaneously supplied into the reaction tube 6, and as shown in FIG. 12C, the ZnSe: N layer 22 is formed.
Is grown epitaxially thinly.

Next, at time t = t ₃ , DM
DMSe while maintaining the supply of Zn and Di-PNH
The supply of water and suspend the growth. During the interruption of the growth, an adsorption layer 24 of Zn and N is formed on the surface of the ZnSe: N layer 22, as shown in FIG. 12D.

Next, at time t = t ₄ , the supply of DMSe into the reaction tube 6 is restarted, and this DSe is supplied until time t = t _5.
Continue to supply MSe. As a result, all of DMZn, DMSe and Di-PNH are simultaneously supplied into the reaction tube 6, and the ZnSe: N layer 22 is again epitaxially grown thin as shown in FIG. 12E.

As described above, after the growth is interrupted to form the adsorption layer 24 of Zn and N, the step of epitaxially growing the ZnSe: N layer 22 on the thin layer is repeated as many times as necessary to obtain the required thickness as a whole. ZnS
e: The N layer 22 is epitaxially grown.

FIG. 14 shows the result of measuring the photoluminescence spectrum of the ZnSe: N layer 22 epitaxially grown as described above at 4.2K. However,
The growth temperature is 450 ° C., and the pressure in the reaction tube 6 is 650 Torr.
r. Also, DMZn, DMSe and Di-PN
The supply amounts of H were 5 μmol / min and 10 μmol, respectively.
/ Min and 75 μmol / min. Further, during the growth, the supply of DMSe was performed intermittently at intervals of 2 seconds and 4 seconds, thereby interrupting the growth. It should be noted that the full scale on the vertical axis in FIG. 14 is different from the full scale on the vertical axis in FIGS.

When FIG. 14 is compared with FIG. 4, also in FIG. 14, the DAP light emission is seen at the same or higher intensity as in FIG. That is, although the supply amount of Di-PNH as the p-type dopant used at the time of growth is half, Z grown by the growth method according to the second embodiment is used.
The intensity of DAP emission of the nSe: N layer 22 is DMZn, D
The intensity of the DAP emission of the ZnSe: N layer 22 grown by the growth method according to the first embodiment in which the growth is performed while simultaneously supplying all of MSe and Di-PNH is substantially equal to or greater than that. This indicates that the growth method according to the second embodiment has a higher N incorporation efficiency and a higher N doping efficiency than the growth method according to the first embodiment.

As described above, according to the growth method of the second embodiment, not only Di-PNH is used as the p-type dopant, but also DMZn, S
While simultaneously supplying all of DMSe as the e raw material and Di-PNH as the p-type dopant, ZnSe: N
A step of growing the layer 22, supplying DMZn and Di
-The supply of DMSe is interrupted while the supply of PNH is maintained to interrupt the growth, so that the N and Zn adsorption layers 2
Since the step of forming 4 is alternately repeated,
The efficiency of incorporation of N into ZnSe can be increased,
Thereby, the desired thickness of Z, which is heavily doped with N, is
An nSe: N layer 22, that is, a p-type ZnSe layer having a high acceptor concentration can be grown.

Here, the effect of annealing the ZnSe: N layer after epitaxially growing the ZnSe: N layer will be described. To investigate this effect, a 2 μm thick ZnSe:
After epitaxially growing the N layer in the same manner as in the first embodiment, a sample was prepared in which a 0.1 μm thick silicon dioxide film (SiO ₂ film) was formed on this ZnSe: N layer by a vacuum evaporation method. However, the growth temperature is 450 ° C., and the pressure in the reaction tube 6 is 650 Torr. Also, DMZn as a Zn raw material, DMSe as a Se raw material and p
The supply amounts of Di-PNH as the type dopant are 9.53 μmol / min, 38.36 μmol / min, and 141 μmol / min, respectively. Note that the SiO ₂ film formed on the ZnSe: N layer is made of ZnSe:
This is for preventing N in the N layer from being eliminated. Next, the sample prepared in this manner was subjected to a radio frequency (RF) heating type annealing apparatus (not shown) by using
RTA (Rapid Thermal Annealin) at 0 ° C for 10 seconds
g), that is, rapid annealing was performed. Thereafter, the SiO ₂ film was removed by etching with hydrofluoric acid.

FIG. 15 shows ZnSe before and after annealing.
The result of measuring the photoluminescence spectrum of the N layer at 4.2K is shown. As shown in FIG. 15, DAP emission was hardly observed before annealing, whereas
After annealing at 00 ° C. for 10 seconds, DAP emission is remarkably exhibited. This is because N in the ZnSe: N layer epitaxially grown under the above-mentioned growth conditions was hardly activated before annealing, but N in the ZnSe: N layer was activated by annealing. can do.

FIG. 16 shows the result of obtaining the effective acceptor concentration (N _A -N _D ) of this sample in the depth direction from the surface of the ZnSe: N layer by the same method as described in the first embodiment. . From this, N _A −N _{D １1} × 10 ¹⁷ cm
It turns out that it is ^-3 . The value of the effective acceptor density is one digit higher than the conventional value.

As described above, by performing annealing after the epitaxial growth of the ZnSe: N layer, this ZnSe: N
The N in the N layer can be activated, so that the ZnSe: N layer having an extremely high acceptor concentration, ie, p
It can be seen that a type ZnSe layer can be obtained.

Next, a description will be given of a third embodiment in which the present invention is applied to the manufacture of a semiconductor laser using a II-VI group compound semiconductor. The semiconductor laser manufactured according to the third embodiment is a so-called SCH (Separate Confineme).
nt Heterostructure).

FIGS. 17 and 18 show a semiconductor laser manufactured according to the third embodiment. Here, FIG.
Is a cross-sectional view perpendicular to the cavity length direction of this semiconductor laser,
FIG. 18 shows a cross-sectional view of the semiconductor laser parallel to the resonator length direction.

As shown in FIGS. 17 and 18, in the method of manufacturing a semiconductor laser according to the third embodiment,
First, an MOCVD method including a step of interrupting the growth by a flow modulation method similar to that of the above-described second embodiment on an (100) -oriented n-type GaAs substrate 31 doped with silicon (Si) as a donor impurity, for example. Thus, for example, n-type ZnSe buffer layer 32 doped with iodine (I) as a donor impurity, for example, n-type Zn _1-p Mg _p S _q Se doped with I as a donor impurity
_1-q cladding layer 33, for example, n-type ZnSe optical waveguide layer 34 doped with I as a donor impurity, for example, intrinsic (i
(Type) Active layer 3 composed of Zn _1-z Cd _z Se quantum well layer
5, for example, p doped with N as an acceptor impurity
Type ZnSe optical waveguide layer 36, for example, p-type N doped as an acceptor impurity _{Zn 1-p Mg p S q} Se 1-q cladding layer 37, for example, p-type N doped as an acceptor impurity ZnS _v Se _{1- The v} layer 38, for example, a p-type ZnSe contact layer 39 doped with N as an acceptor impurity, for example, a quantum well layer made of p-type ZnTe doped with N as an acceptor impurity and the p-type Z
p-type ZnTe in which barrier layers made of nSe are alternately stacked
/ ZnSe multiple quantum well (MQW) layer 40 and, for example, p-type ZnTe doped with N as an acceptor impurity.
The contact layers 41 are sequentially epitaxially grown. p
The type ZnTe / ZnSe MQW layer 40 will be described later in detail.

In this case, in the epitaxial growth of the n-type ZnSe buffer layer 32 and the n-type ZnSe optical waveguide layer 34, for example, DMZn is used as a Zn raw material, DMSe is used as a Se raw material, and ethyl iodide is used as a dopant for I. In the epitaxial growth of the n-type Zn _1-p Mg _p S _q Se _1-q cladding layer 33, for example, Zn
DMZn as a raw material, bismethylcyclopentadienyl magnesium ((MeCp) ₂ Mg) as a Mg raw material,
Diethyl sulfur (DES) is used as the S raw material, and DMSe and ethyl iodide are used as the dopant for the Se raw material. Further, in the epitaxial growth of the active layer 35 composed of the i-type Zn _1-z Cd _z Se quantum well layer, for example, DMZn is used as a Zn material, dimethylcadmium (DMCd) is used as a Cd material, and DMSe is used as a Se material.
Is used.

The p-type ZnSe optical waveguide layer 36 and the p-type ZnSe
Contact layer 39 and p-type ZnTe / ZnSe MQW
In the epitaxial growth of the p-type ZnSe layer of the layer 40, for example, DMZn is used as a Zn material, DMSe is used as a Se material, and Di-PNH is used as a dopant for N. p-type Zn _1-p Mg _p S _q Se _1-q cladding layer 37
In the epitaxial growth of, for example, DMZn as a Zn raw material, (MeCp) ₂ Mg, S
DES is used as a raw material, DMSe is used as a Se raw material, and Di-PNH is used as a dopant for N. Also, p-type Z
In the epitaxial growth of the nS _v Se _1-v layer 38, for example, DMZn is used as a Zn source, and H
Di-PNH is used as a dopant for DMSe and N as ₂ S and Se raw materials. Furthermore, p-type ZnTe / Z
The p-type ZnTe layer and the p-type ZnT of the nSe MQW layer 40
In the epitaxial growth of the e-contact layer 41,
For example, DMZn is used as a Zn raw material, diethyl tellurium (DETe) is used as a Te raw material, and D is used as a dopant of N.
i-PNH is used.

In the epitaxial growth of the n-type ZnSe buffer layer 32 and the n-type ZnSe optical waveguide layer 34, a step of growing while simultaneously supplying DMZn, DMSe and ethyl iodide, and a step of supplying DMZn and ethyl iodide, for example. And the step of interrupting the growth by interrupting the supply of DMSe while maintaining the above. In the epitaxial growth of the n-type _{Zn 1-p Mg p S q} Se 1-q cladding layer 33, DMZn, (MeC
p) a step of growing while simultaneously supplying ₂ Mg, DES, DMSe and ethyl iodide;
The step of interrupting the growth by interrupting the supply of DES and DMSe while maintaining the supply of (MeCp) ₂ Mg and ethyl iodide is repeated.

Further, the p-type ZnSe optical waveguide layer 36, the p-type ZnSe contact layer 39, and the p-type ZnTe / ZnS
In the epitaxial growth of the p-type ZnSe layer of the eMQW layer 40, the growth is performed while simultaneously supplying DMZn, DMSe, and Di-PNH, and the supply of DMSe is interrupted while the supply of DMZn and Di-PNH is maintained. The step of interrupting the growth is repeated. Furthermore, in the epitaxial growth of the p-type Zn _1-p Mg _p S _q Se _1-q cladding layer 37, DMZ
n, (MeCp) ₂ Mg, DES, DMSe and Di
A step of performing growth while simultaneously supplying PNH;
Zn, repeatedly performing step of performing growth interruption by performing supply interruption of DES and DMSe while maintaining the supply of (MeCp) ₂ Mg and Di-PNH. Also,
In the epitaxial growth of the p-type ZnS _v Se _1-v layer 38, DMZn, DES, DMSe and Di-PN
Growth while supplying H simultaneously, and DES and D while maintaining the supply of DMZn and Di-PNH.
The step of interrupting the growth by interrupting the supply of MSe is repeated. Furthermore, p-type ZnTe / ZnSeM
In the epitaxial growth of the p-type ZnTe layer and the p-type ZnTe contact layer 41 of the QW layer 40, DMZ
The step of performing growth while simultaneously supplying n, DETe and Di-PNH, and the step of interrupting growth by interrupting the supply of DETe while maintaining the supply of DMZn and Di-PNH are repeatedly performed.

Next, a stripe-shaped resist pattern (not shown) having a predetermined width is formed on the p-type ZnTe contact layer 41, and the resist pattern is used as a mask to form the p-type ZnS _v Se _1-v layer 38. Etching is performed, for example, by a wet etching method to a certain depth in the thickness direction. Thus, p-type ZnS _v upper portion of Se _1-v layer 38, p-type ZnSe contact layer 39, p-type ZnTe / Z
nSe MQW layer 40 and p-type ZnTe contact layer 4
1 is patterned in a stripe shape. The width of the stripe portion is, for example, 5 μm.

Next, an alumina (Al ₂ O ₃ ) film having a thickness of, for example, 300 nm was vacuum-deposited on the entire surface while leaving the resist pattern used for the above-mentioned etching, and this resist pattern was formed thereon. It is removed together with the Al ₂ O ₃ film (lift-off). As a result, the insulating layer 42 made of the Al ₂ O ₃ film is formed only on the p-type ZnS _v Se _{1 -v} layer 38 other than the above-mentioned stripe portion.

Next, the thickness of, for example, 1 is formed on the entire surface of the stripe-shaped p-type ZnTe contact layer 41 and the insulating layer 42.
A p-side electrode 43 composed of a Pd / Pt / Au electrode is formed by sequentially vacuum-depositing a 0 nm Pd film, for example, a Pt film having a thickness of 100 nm, and an Au film having a thickness of, for example, 300 nm,
Thereafter, heat treatment is performed as necessary, and the p-side electrode 43 is formed.
Is brought into ohmic contact with the p-type ZnTe contact layer 41. The portion where the p-side electrode 43 is in contact with the p-type ZnTe contact layer 41 becomes a current path. On the other hand, on the back surface of the n-type GaAs substrate 31, an n-side electrode 44 such as an In electrode is formed.

Next, after the n-type GaAs substrate 31 on which the laser structure has been formed as described above is cleaved into a bar shape to form both resonator end faces, a front surface from which laser light is extracted by, for example, a vacuum evaporation method. Al ₂
A multilayer film including the O ₃ film 45 and the Si film 46 is formed, and a multilayer film in which the Al ₂ O ₃ film 45 and the Si film 46 are repeated for two periods is formed on the end face of the resonator on the rear side where laser light is not extracted. Form. Here, Al ₂ O ₃ film 45 and the Si
The thickness of the multilayer film composed of the film 46 is selected such that the optical distance multiplied by the refractive index becomes 1/4 of the oscillation wavelength of the laser light. By applying such an end face coating, for example, the reflectance of the front end face is 70%,
The reflectance of the rear end face can be made 95%. After the end face coating is performed in this manner, the bar is cleaved into chips and packaging is performed.

In the semiconductor laser according to the third embodiment, the i-type Zn ₁ -z Cd _z Se quantum well layer constituting the active layer 35 preferably has a thickness of 2 to 20 nm, for example, 9 n.
m.

In this case, n-type Zn _1-p Mg _p S _q
Se _1-q cladding layer 33 and the p-type Zn _1-p Mg p S _q
The Mg composition ratio p of the Se _1-q cladding layer 37 is, for example, 0.0
9, and the S composition ratio q is, for example, 0.18, and the energy gap E _{g at} that time is about 2.94 eV at 77K. N-type Zn _1-p Mg _p S _q Se _1-q having these Mg composition ratio p = 0.09 and S composition ratio q = 0.18
Cladding layer 33 and p-type Zn _1-p Mg _p S _q Se _1-q
The cladding layer 37 is lattice-matched with GaAs. The Cd composition ratio z of the i-type Zn ₁ -z Cd _z Se quantum well layer forming the active layer 35 is, for example, 0.19, and the energy gap E _{g at} that time is about 2.54 eV at 77K.
At this time, n-type _{Zn 1-p Mg p S q} Se 1-q cladding layer 33 and the p-type _{Zn 1-p Mg p S q} Se 1-q constituting the cladding layer 37 and the active layer 35 i-type Zn _1- Difference ΔE in energy gap E _g between _z Cd _z Se quantum well layer
_g is 0.40 eV. Note that the value of the energy gap E _g at room temperature is the energy gap E _g at 77K.
from the value of _g can be determined by subtracting the 0.1eV.

[0084] The thickness of the n-type _{Zn 1-p Mg p S q} Se 1-q cladding layer 33 is, for example 0.8 [mu] m, an n-type ZnSe
The thickness of the optical waveguide layer 34 is, for example, 60 nm, the thickness of the p-type ZnSe optical waveguide layer 36 is, for example, 60 nm, and the p-type Zn _1-p Mg
The thickness of the _p S _q Se _1-q cladding layer 37 is, for example, 0.6μ
m, the thickness of the p-type ZnS _v Se _1-v layer 38 is, for example, 0.6
μm, the thickness of the p-type ZnSe contact layer 39 is, for example, 4
The thickness of the p-type ZnTe contact layer 11 is 5 nm, for example, 70 nm.

Further, the thickness of the n-type ZnSe buffer layer 32 is small because there is a lattice mismatch between ZnSe and GaAs. The thickness is selected to be sufficiently smaller than the critical thickness of ZnSe (〜100 nm) in order to prevent the occurrence of dislocation during the epitaxial growth of the layer 32 and each layer thereon, but is selected here to be, for example, 33 nm.

Note that p-type Zn_1-pMg_pS_qSe_1-qK
P-type ZnS on the lad layer 37_vSe _1-vLayer 38
P-type Zn_1-pMg_pS_qSe_1-qCladding layer
37, function as a second p-type cladding layer, p-type
Zn_1-pMg_pS_qSe_1-qLattice alignment with cladding layer 37
Function to integrate the laser chip onto the heat sink.
For solder creeping up on the chip end surface during und
Function as a spacer layer to prevent short circuit
It has one or more functions. p-type Zn_1-p
Mg_pS_qSe_1-qThe Mg composition ratio p of the cladding layer 37 and
Although there is a trade-off with the S composition ratio q, this p-type ZnS_v
Se_1-vThe S composition ratio v of the layer 38 is preferably 0 <v ≦ 0.1.
Or 0.06 ≦ v ≦ 0.08.
In addition, p-type Zn_1-pMg_pS_qSe_1-qClad layer 37
The optimal S composition ratio v for obtaining lattice matching of
is there.

The above p-type ZnTe / ZnSe MQW layer 4
The reason why 0 is provided is that when the p-type ZnSe contact layer 39 and the p-type ZnTe contact layer 41 are directly joined, a large discontinuity occurs in the valence band at the junction interface. This is to effectively eliminate this barrier since it acts as a barrier to holes injected into the substrate.

That is, the upper limit of the carrier concentration in p-type ZnSe is usually about 5 × 10 ¹⁷ cm ⁻³ ,
The carrier concentration in the type ZnTe can be 10 ¹⁸ cm ⁻³ or more. Also, p-type ZnSe / p-type ZnTe
The magnitude of the valence band discontinuity at the interface is about 0.5 eV
It is. In the valence band of such a p-type ZnSe / p-type ZnTe junction, assuming that the junction is a step junction, a width of W = (2εφ _T / qN _A ) ^1/2 (1) on the p-type ZnSe side. Over the band. Here, ε is the dielectric constant of ZnSe, φ _T is p-type ZnSe / p-type ZnTe
The size of the discontinuity of the valence band at the interface (about 0.5e
V).

When W is calculated in this case using equation (1), W = 32 nm. FIG. 19 shows how the top of the valence band changes along the direction perpendicular to the p-type ZnSe / p-type ZnTe interface at this time. However, it is approximated that the Fermi level of p-type ZnSe and p-type ZnTe coincides with the top of the valence band. As shown in FIG. 19, in this case, the valence band of p-type ZnSe is p-type ZSe.
It is bent downward (low energy side) toward nTe. The change in the downwardly convex valence band acts as a potential barrier for holes injected from the p-side electrode 43 into the p-type ZnSe / p-type ZnTe junction.

The problem is that the p-type ZnSe contact layer 3
9 and the p-type ZnTe contact layer 41
The problem can be solved by providing the e / ZnSe MQW layer 40. This p-type ZnTe / ZnSe MQW layer 4
0 is specifically designed as follows, for example.

FIG. 20 shows the relationship between the width L _W of the p-type ZnTe quantum well in a single quantum well having a structure in which a quantum well layer made of p-type ZnTe is sandwiched on both sides by a barrier layer made of p-type ZnSe. The results obtained by calculating how the one quantum level E ₁ changes by quantum mechanical calculation for a well-type potential of a finite barrier are shown. However, in this calculation, assuming the effective mass m _{h of} holes in p-type ZnSe and p-type ZnTe as the mass of electrons in the quantum well layer and the barrier layer, 0.6 m ₀ (m ₀ : electron mass in vacuum) And the depth of the well is 0.5 eV.

FIG. 20 shows that the first quantum level E formed in the quantum well is reduced by reducing the width L _W of the quantum well.
It can be seen that ₁ can be increased. p-type ZnTe
The / ZnSe MQW layer 40 is designed utilizing this fact.

In this case, the bending of the band generated over the width W from the p-type ZnSe / p-type ZnTe interface to the p-type ZnSe side is a quadratic function of the distance x (FIG. 19) from the p-type ZnSe / p-type ZnTe interface. φ (x) = φ _T {1− (x / W) ² } (2) Therefore, p-type ZnTe / ZnSe MQW
According to the design of the layer 40, the first quantum level E ₁ formed in each of the quantum well layers made of p-type ZnTe is based on the equation (2), and the first quantum level E ₁ is the top of the valence band of p-type ZnSe and p-type ZnTe. consistent with energy, yet can be performed by changing stepwise the equal manner L _W each other.

FIG. 21 shows a p-type ZnTe / ZnSe MQW
Shows a design example of a quantum well width L _w in a case where the width L _B of the barrier layer made of p-type ZnSe in the layer 40 and 2 nm. In this case, the acceptor concentration N _A of the p-type ZnSe contact layer 39 is 5 × 10 ¹⁷ cm ^−3, and the acceptor concentration N _A of the p-type ZnTe contact layer 41 is 1 × 10 ¹⁹ cm ⁻³ . In this case, as shown in FIG.
The width L _w of each of the quantum wells is adjusted from the p-type ZnSe contact layer 39 to the p-type ZnT so that the first quantum level E ₁ matches the Fermi level of p-type ZnSe and p-type ZnTe.
To the e-contact layer 41, L _w = 0.3 nm;
4 nm, 0.5 nm, 0.6 nm, 0.8 nm, 1.1
nm and 1.7 nm.

[0095] Incidentally, when designing the widths L _w of the quantum well, strictly speaking, level of the respective quantum wells must consider the interaction of them for binding to each other, also, the quantum Although the effect of distortion due to lattice mismatch between the well layer and the barrier layer must also be taken into account, it is in principle sufficiently possible to set the quantum levels of the multiple quantum wells flat as shown in FIG.

In FIG. 21, holes injected into the p-type ZnTe are converted into p-type ZnSe by resonance tunneling through the first quantum level E ₁ formed in each quantum well of the p-type ZnTe / ZnSe MQW layer 40. Therefore, the potential barrier at the p-type ZnSe / p-type ZnTe interface is effectively eliminated.

As described above, according to the third embodiment,
As in the second embodiment, when epitaxial growth of each p-type layer forming the laser structure is performed, Di-PNH is used as a p-type dopant, and the growth is interrupted by interrupting the supply of the raw material of the group VI element. , The acceptor concentration of these p-type layers can be sufficiently increased. In addition, when epitaxial growth of each n-type layer forming the laser structure is performed, the step of interrupting the growth by interrupting the supply of the raw material of the group II element also ensures that the donor concentration of these n-type layers is sufficiently high. Can be. This makes it possible to realize a high-performance semiconductor laser that can emit light at a short wavelength and has a low threshold current density. More specifically, for example, a green-emitting semiconductor laser capable of continuous oscillation at room temperature can be realized. It is also possible to reduce the applied voltage required for laser oscillation.

Although the embodiments of the present invention have been specifically described above, the present invention is not limited to the above-described embodiments, and various modifications based on the technical idea of the present invention are possible.

For example, in the second embodiment, S
Although the case where the present invention is applied to the manufacture of a semiconductor laser having a CH structure has been described, the present invention can also be applied to the manufacture of a semiconductor laser having a DH structure (Double Heterostructure).

Further, in the second embodiment described above, the case where the present invention is applied to the manufacture of a semiconductor laser has been described. However, the present invention is applied to the manufacture of a light emitting diode using a II-VI group compound semiconductor. It is also possible to apply to the manufacture of various semiconductor devices using II-VI compound semiconductors other than these light emitting elements.

In the first and second embodiments described above, a GaAs substrate is used as a compound semiconductor substrate.
An aP substrate or the like may be used.

Note that the II-VI group compound semiconductors are
As a p-type dopant at the time of epitaxial growth by the VD method or the MBE method using a gas material, for example, another atom is a double bond to the N atom such as cyanamide (HN = C = NH). A bound organic compound may be used.

The organic compound used as the p-type dopant in the present invention, that is, contains at least one nitrogen atom, and has a molecular weight of at least 12
The organic compound to which at least two larger groups are bonded is a compound semiconductor containing nitrogen, for example, GaN (II
It can be used as an N source when growing a group IV-compound semiconductor) by vapor phase growth.

[0104]

As described above, according to the present invention,
A nitrogen-containing compound semiconductor containing at least one nitrogen atom and having at least two groups having a molecular weight greater than at least 36 bonded to the nitrogen atom. A nitride III-V compound semiconductor can be easily grown.

[Brief description of the drawings]

FIG. 1 shows an MOCV used in a first embodiment of the present invention.
It is an approximate line figure showing the composition of D device.

FIG. 2 is a sequence diagram illustrating a method for growing p-type ZnSe according to a first embodiment of the present invention.

FIG. 3 is a cross-sectional view for explaining a method of growing p-type ZnSe according to the first embodiment of the present invention.

FIG. 4 is a graph showing an example of a measurement result of a photoluminescence spectrum of a p-type ZnSe layer grown by the method for growing a p-type ZnSe according to the first embodiment of the present invention.

[Figure 5] using the t-BNH ₂ as a p-type dopant M
5 is a graph showing an example of a measurement result of a photoluminescence spectrum of a p-type ZnSe layer grown by an OCVD method.

FIG. 6 is a cross-sectional view of a sample used for quantitatively evaluating the acceptor concentration of a p-type ZnSe layer grown by the method for growing a p-type ZnSe according to the first embodiment of the present invention by a CV measurement method. is there.

FIG. 7 is a plan view of a sample used for quantitatively evaluating the acceptor concentration of a p-type ZnSe layer grown by the method for growing a p-type ZnSe according to the first embodiment of the present invention by a CV measurement method. is there.

FIG. 8 is a graph showing C- values obtained by using the samples shown in FIGS.
It is a graph which shows an example of the result of V measurement.

9 is a graph showing an example of a profile of an effective acceptor concentration obtained from the result of the CV measurement shown in FIG.

FIG. 10 is a graph showing the relationship between the acceptor concentration of p-type ZnSe and the photoluminescence intensity.

FIG. 11 is a sequence diagram illustrating a method for growing p-type ZnSe according to a second embodiment of the present invention.

FIG. 12 is a sectional view illustrating a method for growing p-type ZnSe according to a second embodiment of the present invention.

FIG. 13 shows NH generated by thermal decomposition of Di-PNH.
Is compared with a state in which NH ₂ generated by thermal decomposition of t-BNH ₂ is bonded to a Zn atom on the Zn plane of the ZnSe crystal. FIG.

FIG. 14 is a graph showing an example of a measurement result of a photoluminescence spectrum of a p-type ZnSe layer grown by a p-type ZnSe growth method according to a second embodiment of the present invention.

FIG. 15 is a graph showing an example of a measurement result of a photoluminescence spectrum of a p-type ZnSe layer before and after annealing.

FIG. 16 is a graph showing an example of a profile of an effective acceptor concentration obtained for a sample from which the photoluminescence spectrum shown in FIG. 15 was obtained.

FIG. 17 is a sectional view of a semiconductor laser manufactured by a semiconductor laser manufacturing method according to a third embodiment of the present invention, which is perpendicular to the resonator length direction.

FIG. 18 is a sectional view of a semiconductor laser manufactured by a semiconductor laser manufacturing method according to a third embodiment of the present invention, which is parallel to the resonator length direction.

FIG. 19 is an energy band diagram showing a valence band near a p-type ZnSe / p-type ZnTe interface.

FIG. 20 is a graph showing a change in the first quantum level E ₁ of the quantum well with respect to the width L _w of the quantum well made of p-type ZnTe.

FIG. 21 is a schematic diagram illustrating a design example of a p-type ZnTe / ZnSe MQW layer in a semiconductor laser according to a third embodiment of the present invention.

[Explanation of symbols]

 21: semi-insulating GaAs substrate, 22: ZnS
e: N layer, 24 ... adsorption layer of Zn and N, 31 ...
・ N-type GaAs substrate, 32 ... n-type ZnSe buffer
Layer, 33... N-type Zn_1-pMg_pS_qSe_1-qCrack
Layer, 34... N-type ZnSe optical waveguide layer, 35.
Layer, 36 ... p-type ZnSe optical waveguide layer, 37 ... p
Type Zn_1-pMg_pS_qSe_1-qCladding layer, 38 ...
p-type ZnS _vSe_1-vLayer, 39 ... p-type ZnSe capacitor
Tact layer, 40 ... p-type ZnTe / ZnSe MQW
Layer, 41 ... p-type ZnTe contact layer, 42 ...
Insulating layer, 43 ... p-side electrode, 44 ... n-side electrode

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5F045 AA04 AB22 AC08 AD08 AE25 AF04 BB08 BB16 CA12 DA53 5F073 AA03 AA45 AA71 AA74 AA83 CA02 CA22 CB19 CB20 DA05 DA35

Claims (2)

[Claims] An organic compound containing at least one nitrogen atom and having at least two groups having a molecular weight greater than at least 36 bonded to the nitrogen atom is used as a nitrogen source to vapor-deposit a compound semiconductor containing nitrogen. A method for growing a compound semiconductor containing nitrogen, the method comprising: growing a compound semiconductor containing nitrogen. 2. A nitride III-V compound semiconductor using an organic compound containing at least one nitrogen atom and having at least two groups having a molecular weight greater than at least 36 bonded to the nitrogen atom as a nitrogen source. Is grown by a vapor phase epitaxy method.