JP3467988B2 - Semiconductor manufacturing method and semiconductor manufacturing apparatus - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a semiconductor manufacturing method and a semiconductor manufacturing apparatus.

[0002]

2. Description of the Related Art In recent years, AlN, GaN, AlGaN, G
Semiconductor compounds having a wide bandgap such as aInN and InN have attracted attention as materials applicable to blue LEDs, blue LDs, and visible light emitting devices. These Nitride Systems III [IUPAC (International Union of Pure and Applied Chemistry) has a family number of 13 according to the revised 1989 Inorganic Chemistry Nomenclature]
NH ₃ and N ₂ are used as a group V element source in the production of a group V semiconductor compound, which is a group number 15 according to the revised inorganic chemical nomenclature of 1989 of IUPAC, but NH ₃ and N ₂
Is more stable and inactive than other group V element sources used in the production of III-V compound semiconductors, such as AsH ₃ and PH ₃ . Therefore, metal organic chemical vapor deposition (MOC)
In the case of forming a nitride-based III-V semiconductor compound film on a substrate by VD), the substrate temperature is 900 to 1200.
Adjusted to ° C.

On the other hand, 900 ° C at which good quality GaN grows
Since In is hardly taken into the crystal at a high substrate temperature of up to 1200 ° C., the substrate temperature is lowered when preparing a mixed crystal containing In. However,
With this method, the film quality is sacrificed, and it is difficult to obtain a good-quality mixed crystal containing 10% or more In. Also,
In the method of changing the substrate temperature, when forming a film at high temperature,
It is practically difficult to fabricate an element such as a multilayer film or a superlattice because element diffusion or the like of a film formed under this film and formed at a low temperature may occur.

Therefore, as a method of lowering the growth temperature,
High frequency discharge (JM Van Hore et al., J. Cryst. Growth 150
(1995) 908), N ₂ or N as a group V element source by microwave discharge or electron cyclotron resonance.
H ₃ is put into a plasma state, and in this remote plasma II
There is a method of forming a film by introducing an organometallic compound containing a Group I element (A. Yoshida, New Functionali
ty materials, Vol.C.183-188 (1993), S.Zembutsu
App.Phys.Left.48,870). As a device for carrying out this method, one plasma generating means continuous to the reactor, and a group V element source such as N ₂ gas is supplied to this plasma generating means from the side opposite to the reactor side. A semiconductor manufacturing apparatus including a first supply means and a second supply means for supplying an organometallic compound containing a Group III element to a reactor side of a plasma generation means has been conventionally known.

[0005]

When a mixed crystal is produced using this semiconductor manufacturing apparatus, a mixture containing two or more kinds of organometallic compounds such as trimethylgallium and trimethylindium is provided by the second supply means. Supply gas. However, since the binding energies of these organometallic compounds are different, when a mixed gas of these organometallic compounds is introduced into plasma, one of them is easily decomposed selectively, and the ratio of the two in the mixed gas is adjusted. However, there are problems that it is difficult to control the composition of the formed film and that the formed film contains carbon impurities derived from an organometallic compound that is less likely to decompose.

Further, when laminating films of different elemental systems using the above semiconductor manufacturing apparatus, it is necessary to switch the source gas, and the active species concentration on the substrate surface becomes a desired value after switching the source materials. It took a few minutes to a dozen minutes, and it was not possible to form a film during this period.

The present invention is intended to improve the drawbacks of the conventional semiconductor manufacturing method and semiconductor manufacturing apparatus using such remote plasma, and to produce high-quality and high-performance semiconductors and semiconductor devices in a short time with high productivity. A semiconductor manufacturing method and manufacturing apparatus are provided.

[0008]

As a result of the earnest efforts of the present inventor, it was found that the above problems can be achieved by controlling the film forming process and the reaction process using plasma, and the present invention has been completed. According to the method of manufacturing a semiconductor according to the first aspect of the present invention, the group V element source in the plasma state contains a group III element.
A first reaction step of reacting an organometallic compound comprising:
Second, in which an auxiliary material is reacted with a product generated by the reaction
Including the group V element and the group III element
A film forming step of forming a semiconductor compound on a substrate . According to a second aspect of the present invention, there is provided a semiconductor manufacturing method, which comprises a first plasma generating step of bringing a group V element source containing a group V element into a plasma state, and
II.
An organometallic compound containing a group I element is added to
A step of forming a reaction product containing the group III element,
Second, to put auxiliary material to prevent plasma from falling
Of the plasma generation step and the auxiliary material in the plasma state
And a film forming step of forming a semiconductor compound containing the group V element and the group III element on the substrate by adding the product generated by the reaction step .

According to a third aspect of the present invention, there is provided a semiconductor manufacturing method, wherein a first plasma generating step of bringing a group V element source containing a group V element into a plasma state and the first plasma generating step are generated. A second plasma that brings a group V element source into a plasma state separately and simultaneously with the first addition step of adding a gaseous organometallic compound containing a group III element to the plasma and the first plasma generation step. II in the plasma generation step and the plasma generated in the second plasma generation step
Used in the second addition step of adding a gaseous organometallic compound containing a group III element different from the group I element and the group III element added in the first addition step and the first plasma generation step The semiconductor compound containing the group V element and the group III element and the second group added in the second adding step.
Film forming step of forming a mixed crystal with the semiconductor compound containing the group V element used in the plasma generating step on the substrate.

[0010] In these inventions, further or added gaseous raw material p n control, or use high-frequency discharge and / or microwave discharge, the group V element to be used and nitrogen plasma generated be able to.

According to a ninth aspect of the present invention, there is provided a nitride semiconductor manufacturing apparatus, wherein a reactor for forming a semiconductor film on a substrate and a reactor provided inside the reactor are provided. a heating holding means for heating while holding, continuously and <br/> first supply means for supplying a group V element source, and the first supply hand Dan及 beauty the reactor, the supplied group V element you the source to the plasma state
A first plasma generating means, and second supply means for supplying an organic metal compound containing a III group element prior Symbol reactor side of the first plasma generating means, into a plasma state
Third supply means for supplying a first gas for
It is continuously supplied with the third supply means and the reactor.
Second plasma generation that turns the first gas into a plasma state
Means and the reactor side of the second plasma generating means
And a fourth supply means for supplying the second gas .

Further, the semiconductor according to the invention of claim 10
The body manufacturing apparatus is used to form a semiconductor film on a substrate.
The reactor, partition means for partitioning the interior of the reactor, and the reactor
It is provided inside the reactor and holds the substrate and heats it.
The holding means and the heating holding means are separated by the partition means.
The heating and holding so that it passes through the entire space partitioned by
Moving means to move the means and to put into a plasma state
First supply means for supplying a first gas of
And continuous with each of the first supply means and the reactor
The supplied first gas into a plasma state.
Plasma generating means and each of the plurality of plasma generating means
A plurality of first source gases for supplying the second source gas to the reactor side, respectively.
2 supply means, and by the partition means
Each of the partitioned spaces has at least one plasma
It is characterized by being continuous with the generating means.

Further, the above invention may further comprise an exhaust means continuous to all of the spaces partitioned by the partition means.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

FIG. 1 shows a schematic structure of a semiconductor manufacturing apparatus 10 according to a first embodiment of the present invention. This semiconductor manufacturing apparatus 10 includes a cylindrical reactor 12, first and second raw material activation-supplying units 14 and 16 which are continuous with the reactor 12 through openings 12A and 12B, the reactor 12 and the opening. An exhaust pipe 18 for exhausting gas in the reactor 12, which is continuous through 12C, and is arranged in the reactor 12.
Further, the substrate holder 20 for supporting the substrate and the heater 22 arranged on the side opposite to the substrate installation surface side of the substrate holder 20 are provided.

First and second raw material activating-supplying section 14,
Reference numerals 16 have the same structure, and each has a cylindrical quartz tube 24 which is in communication with the reactor 12 and is arranged on the outer side in the radial direction of the reactor 12, and the opposite side of the quartz tube 24 from the reactor 12. A gas introducing pipe 26 communicating with the quartz pipe 24, a microwave waveguide 28 arranged so as to intersect with the quartz pipe 24, and a quartz pipe 24 on the reactor 12 side from the intersecting position of the quartz pipe 24 and the microwave waveguide 28. And a continuous gas introduction pipe 30. The microwave waveguide 28 has a casing shape, and the quartz tube 2
4 penetrates.

The gas introducing pipes 26 and 30 of the first and second raw material activating-supplying units 14 and 16 are connected to a cylinder or the like as a raw material supplying means (not shown) for supplying the raw material gas. The microwave waveguide 28 is connected to a microwave oscillator using a magnetron (not shown), and discharges in the quartz tube 24. Further, the exhaust pipe 30 is connected to a pump (not shown) serving as an exhaust means, so that the inside of the reactor 12 can be exhausted to a substantially vacuum.

Further, FIG. 2 shows a semiconductor manufacturing apparatus 40 according to a second embodiment of the present invention. The second
In the semiconductor manufacturing apparatuses of the following embodiments, the same configurations as those of the semiconductor manufacturing apparatus 10 according to the first embodiment are designated by the same reference numerals, and description thereof will be omitted.

This semiconductor manufacturing apparatus 40 is provided with a second raw material activation-supply section 42 instead of the second raw material activation-supply section 16 in the semiconductor manufacturing apparatus 10, and a second raw material activation-supply section is provided. In 42, a high frequency coil 44 is used instead of the microwave waveguide 28, and the high frequency coil 44 is wound around the outer circumference of the quartz tube 24 and connected to a high frequency oscillator (not shown).

Semiconductor manufacturing apparatus 10 and semiconductor manufacturing apparatus 4
At 0, for example, the group V element source is supplied from the gas introduction pipe 26 of the first raw material activation-supply unit 14, and the group III element is included from the gas introduction pipe 30 of the first raw material activation-supply unit 14. Supplying an organometallic compound and activating the second raw material-supply unit 1
An auxiliary material for activating the organometallic compound and decomposing or reacting the organic functional group to the outside of the reaction system can be supplied from the gas introduction pipes 26 and 42. Further, for example, the first and second raw material activation-supply units 14, 16 and 4
The group V element source is supplied from the gas introduction pipe 26 of No. 2 and the organometallic compounds containing different Group III elements are supplied from the gas introduction pipes 30 of the first and second raw material activation-supply units 14, 16 and 42 respectively. Can be supplied. Then, in order to change the activation condition of the group V element in accordance with the binding energy of each organometallic compound, the discharge condition, the gas flow rate, etc. can be changed in each raw material activation-supply section. Therefore, by using these semiconductor manufacturing apparatuses 10 and 40, it is possible to form a film with less impurities mixed therein and a film of a high quality mixed crystal.

Further, FIG. 3 shows a semiconductor manufacturing apparatus 50 according to a third embodiment of the present invention. The semiconductor manufacturing apparatus 50 includes a case-shaped reactor 52. In the reactor 52, a plate-shaped partition wall 54 with a gate valve is provided.
Are provided so as to divide the volume in the reactor 52 into two equal parts. Further, in the semiconductor manufacturing apparatus 50, the first raw material activation-supply unit 14 and the first raw material activation-supply unit 14 which are continuous with the reactor 52 on the side of the first space 56 partitioned by the partition wall 54. A second raw material activation-feeding section 16 which is disposed on the same side as the second space 58 and which is partitioned by the partition wall 54 and which is continuous with the reactor 52, and first and second raw material activation-feeding An exhaust pipe 60 arranged on the opposite side of the parts 14 and 16 and continuous with the reactor 52 so as to be continuous with both the first space 56 and the second space 58, and a substrate arranged in the reactor 52. A substrate holder 62 for supporting the
The heater 64 is provided on the side of the substrate holder 62 opposite to the side on which the substrate is installed. The substrate holder 62 and the heater 64 are moved through a gate valve of the partition wall 54 to move the first space 56 and the second space 58 by moving means (not shown).
It is made possible to move integrally between and.

Further, FIG. 4 shows a semiconductor manufacturing apparatus 70 according to a fourth embodiment of the present invention. The semiconductor manufacturing apparatus 70 includes a cylindrical reactor 72.
A circular hole (not shown) is formed at the center of both circular end surfaces (not shown) of the reactor 72.
Penetrates through this hole and is arranged coaxially with the reactor 72. The space between the reactor 72 and the exhaust pipe 74 is sealed with resin or the like. This exhaust pipe 74 has four equal intervals.
Book slits are formed along the axial direction, and the inside of the reactor 72 is exhausted through the slits.

Further, in the reactor 72, four plate-shaped partition walls with a gate valve 76 divide the volume in the reactor 72 into four equal parts, and slits of the exhaust pipe 74 are arranged in each space. Thus, it is provided along the radial direction. Further, the semiconductor manufacturing apparatus 70 has the first raw material activation-supply unit 1 communicating with the first space 78 partitioned by the two partition walls 76.
Second space 8 partitioned by 4 and two partitions 76
The second raw material activation-supply unit 16 communicating with 0, the third raw material activation-supply unit 84 communicating with the third space 82 partitioned by the two partition walls 76, and the two partition walls 76. A fourth raw material activating-supplying section 88 that communicates with a fourth space 86 partitioned by, a substrate holder 92 for supporting the substrate arranged in the reactor 72, and a substrate holder 92.
Heater 90 arranged on the opposite side of the substrate mounting surface side
And The substrate holder 92 and the heater 90 can be integrally moved between the first space 78 to the fourth space 86 via a gate valve of the partition wall 76 by a moving unit (not shown).

The constructions of the third and fourth raw material activation-supplying sections 84 and 88 are the same as the constructions of the first and second raw material activation-supplying sections 14 and 16, and the description thereof will be omitted. .

In the semiconductor manufacturing apparatus 50 and the semiconductor manufacturing apparatus 70, in each space, the discharge power, the flow rate of the activating raw material,
The activation conditions such as the group III organometallic compound gas flow rate can be changed, and when laminating films with different compositions, a substrate holder and heater are installed in the adjacent spaces through the gate valves provided in each partition. By moving the film, films can be continuously formed, and the time required for manufacturing a semiconductor can be shortened.

In the embodiment of the present invention, the method for activating the raw material activating-supplying unit may be any one of high frequency discharge, microwave discharge, electron cyclotron resonance system, and helicon plasma system, and one of them may be used. May be used, or two or more may be used. Further, in the case of high frequency discharge, it may be an inductive coupling type as in the second embodiment or a capacitive type.

In the case where two or more activation methods are used in one space, it is necessary to generate discharges at the same pressure at the same time, and the inside of the microwave waveguide (or the high-frequency waveguide) and the quartz are required. A pressure difference may be provided inside the tube (or inside the reactor). If these pressures are the same,
The excitation energy of the active species can be largely changed by using different raw material activating means, for example, microwave and high frequency discharge, and thus the film quality can be controlled.

In the third and fourth embodiments, one raw material activation-supply section is continuous in the space partitioned by the partition walls, but two or more raw material activations are performed in one space. -Mixed crystals may be formed in each space by making the supply section continuous.

In the above embodiment, the substrate temperature is 20.
C. to 1200.degree. C., preferably 100.degree. C. to 1000.degree. C., and the substrate temperature can be appropriately changed according to the purpose. For example, when gallium nitride is used, it is amorphous when the substrate temperature is low (20 ° C to 300 ° C), crystalline when the substrate temperature is high (400 ° C to 1000 ° C), and intermediate temperature (300 ° C to 400 ° C). In this case, a polycrystalline film can be used.

The substrate used in the present invention may be conductive or insulating, and may be crystalline or amorphous. As the conductive substrate, metals such as aluminum, stainless steel, nickel and chromium and their alloy crystals, Si, GaA
Examples include semiconductors such as s, SiC, and sapphire and single crystals.

The insulating substrate may be a polymer film, glass, ceramic or the like, and the insulating substrate may be made of the above metal or gold, silver, copper or the like by a vapor deposition method, a sputtering method, an ion method. Conductive treatment for forming a film by a plating method or the like is performed.

As the transparent support of the transparent conductive substrate for inputting / outputting light, a transparent inorganic material such as glass, quartz, sapphire; fluororesin, polyester, polycarbonate,
A transparent organic resin film or plate such as polyethylene, polyethylene terephthalate, or epoxy resin; optical fiber, SELFOC optical plate or the like can be used.

As the transparent electrode provided on the transparent support, a transparent conductive material such as ITO, zinc oxide, tin oxide, lead oxide, indium oxide or copper iodide is used, and vapor deposition or ion plating is performed. Those formed by a method such as sputtering, or those formed by forming a metal such as Al, Ni, Au, etc. thin by vapor deposition or sputtering so as to be semi-transparent are used.

As the group V element source introduced from at least one of the gas introduction pipes 26, N ₂ , NH ₃ , NF ₃ and N _{2 are used.}
A gas such as H ₄ , monomethylhydrazine or dimethylhydrazine, or a mixed gas obtained by bubbling these gases with a carrier gas can be used. In addition, PH ₃ , P (C ₄ H
₉ ) ₃ , AsH ₃ , and AsH ₂ C (CH ₃ ) ₃ may be used. Furthermore, even if these group V element sources are used alone,
You may use it in combination.

As the carrier gas, rare gases such as He and Ar, single element gases such as H ₂ and N ₂ , hydrocarbons such as methane and ethane, and halogenated carbon such as CF ₄ and C ₂ F ₆ are used. You can

The organometallic compound containing a Group III element introduced through at least one of the gas introduction pipes 30 is
Trimethyl aluminum, triethyl aluminum, t
A liquid or solid such as butylaluminum, trimethylgallium, triethylgallium, t-butylgallium, trimethylindium, triethylindium, t-butylindium is vaporized and used alone or as a mixed gas bubbled with the carrier gas. can do.

As an auxiliary material for reacting with the organic functional group of the organometallic compound containing the Group III element to bring this organic functional group out of the reaction system, a rare gas such as He, Ne or Ar,
Halogen gas such as H ₂ , Cl ₂ and F ₂ can be used alone or in combination. Further, these auxiliary materials may be mixed with the group V element source and used. The auxiliary material can be appropriately used for controlling the energy of the active species and preventing film defects by making the organic functional group an inactive molecule.

Further, an element for controlling p and n can be introduced from the gas introducing pipe 30 to dope the film.

As elements for n-type, group IA (IUPA)
C of the revised 1989 version of the inorganic chemical nomenclature has a group number of 1), Li, and IB (IUPAC's revised version of the 1989 inorganic chemical nomenclature has a group number of 11): Cu, Ag, and A.
u, Group IIA (IUPAC 1989 revised inorganic chemical nomenclature has a family number of 2) Mg, Group IIB (IUPAC revised 1989 inorganic chemical nomenclature has a family number 12)
Zn, IVA group (Siu, Ge, Sn, P of IUPAC revision number 1989 revised inorganic chemical nomenclature is 14)
b, S, Se, Te of the VIA group (the group number is 16 according to the revised 1989 inorganic chemical nomenclature of IUPAC) can be used. Among them, Si, Ge, and Sn are preferable from the viewpoint of controllability of charge carriers.

Examples of p-type elements include IA group Li and N
a, Cu, Ag, Au of Group IB, Be, Mg of Group IIA,
Ca, Sr, Ba, Ra, IIB group Zn, Cd, Hg,
IVA group C, Si, Ge, Sn, Pb, VIB group (IUP
AC, the revised 1989 Inorganic Chemistry Nomenclature has a family number of 6) Cr, Group VIII Fe (IUPAC, the revised 1989 Inorganic Chemistry Nomenclature has a family number of 8), Co (IUP
AC, the family number according to the revised 1989 version of the inorganic chemistry nomenclature, 9), Ni (the family number according to the IUPAC revised 1989 version of the inorganic chemistry nomenclature) can be used. Above all, Be, Mg, Ca, Zn, and Sr are preferable from the viewpoint of controllability of charge carriers.

As the doping method, SiH ₄ , Si ₂ H ₆ , GeH ₄ , GeF ₄ and SnH ₄ are used for n-type.
For Be type, BeH ₂ , BeCl ₂ , BeC
l ₄ , cyclopentadienyl magnesium, dimethyl calcium, dimethyl strontium, dimethyl zinc, diethyl zinc and the like can be used in a gas state. Further, it can be diffused in the film as an element or incorporated as an ion in the film.

[0042]

EXAMPLES The present invention will be described in detail below based on examples of the present invention. (Example 1) Using the semiconductor manufacturing apparatus 10 of FIG. 1, the cleaned sapphire substrate, quartz substrate, and Si wafer were placed on the substrate holder 20, vacuum exhausted, and heated to 500 ° C. N
₂ Gas is the first raw material activation-gas introduction pipe 2 of the supply unit 14
From No. 6, 500 sccm was introduced into a quartz tube 24 having a diameter of 25 mm, a microwave of 2.45 GHz was set to an output of 300 W, matching was performed with a tuner, and discharge was performed. The reflected wave at this time was 0W. On the other hand, the H ₂ gas is supplied from the gas introduction pipe 26 of the second raw material activation-supply unit 16 to the diameter 25
500 sccm was introduced into the quartz tube 24 of mm, and 2.45
Discharge was performed with a microwave of GHz at an output of 200 W. The reflected wave was 0W. In this state, the vapor of trimethylgallium (TMGa) kept at room temperature was introduced through the gas introduction pipe 30 of the first raw material activation-supply unit 14 directly at 2 sccm through the mass flow controller. At this time, the pressure in the reactor 12 measured by the Baratron vacuum gauge was 0.2 To.
It was rr.

When film formation was carried out for 1 hour and the film composition was measured by XPS, the Ga / N ratio was 1.01, which was a stoichiometric ratio. The half width of the (0002) diffraction peak of the X-ray diffraction spectrum was 50 arcsec. (Example 2) The same apparatus and conditions as in Example 1 were used.
However, biscyclopentadienyl Mg was heated to 50 ° C. and 10 sccm of hydrogen was supplied as a carrier gas to the gas introduction pipe 30 of the supply unit 16. In this way, p-type Ga
An N film was produced. (Example 3) The same apparatus and conditions as in Example 1 were used.
However, silane was diluted with hydrogen (1%) and supplied at 5 sccm to the gas introduction pipe 30 of the supply unit 16 to form an n-type GaN film. (Example 4) Using the same device and the same substrate as in Example 1,
500 sccm of N ₂ gas was introduced into the quartz tube 24 having a diameter of 25 mm from the gas introduction tube 26 of the first raw material activation-supply section 14.
Then, the microwave of 2.45 GHz was set to an output of 300 W, matching was performed with a tuner, and discharging was performed.
The reflected wave at this time was 0W. In addition, the N ₂ gas of the second raw material activation-supply unit 16 is introduced from the gas introduction pipe 26 to a diameter
Introducing 500 sccm into a 5 mm quartz tube 24, 2.4
Discharge was performed with a microwave of 5 GHz and an output of 250 W.
The reflected wave was 0W. In this state, the first raw material activation-
The vapor of trimethylgallium held at room temperature was introduced at 1 sccm from the gas introduction pipe 30 of the supply part 14, and the vapor of trimethylindium was kept at 30 ° C. from the gas introduction pipe 30 of the second raw material activation-supply part 16. 5 sccm to N ₂
50 sccm was introduced together with the carrier gas. At this time, the pressure in the reactor 12 measured by the Baratron vacuum gauge was 0.
It was 3 Torr.

Under these conditions, the decomposition rates of trimethylgallium and trimethylindium were measured using a quadrupole mass spectrometer, and the former was 99.8% and the latter was 99.9%.

Film formation was carried out for 1 hour, and the film composition was measured by RBS (Rutherford backscattering).
It was found that the a / In ratio was 2: 1 and was equal to the introduced gas ratio. The Ga + In / N ratio was 1.05, which was a stoichiometric ratio. The optical gap was 2.6 eV. For the film on the sapphire substrate, (00
02) The full width at half maximum of the diffraction peak was 60 arcsec. (Embodiment 5) The semiconductor manufacturing apparatus 40 of FIG. 2 and the same substrate as in Embodiment 1 were used, and after evacuation, they were heated to 500 ° C. N
₂ Gas is the first raw material activation-gas introduction pipe 2 of the supply unit 14
From No. 6, 500 sccm was introduced into a quartz tube 24 having a diameter of 25 mm, a high frequency of 13.56 MHz was set to an output of 100 W, matching was performed, and discharge was performed. The reflected wave at this time was 0W. Also, N ₂ gas is used to activate the second raw material--
The gas was introduced into the quartz tube 24 having a diameter of 25 mm by 500 sccm from the gas introduction tube 26 of the supply unit 16, and the discharge was performed with the microwave of 2.45 GHz and the output of 250 W. The reflected wave was 0W. In this state, 1 sccm of trimethylgallium vapor held at room temperature is introduced from the gas introduction pipe 30 of the first raw material activation-supply unit 14 to introduce gas from the gas introduction pipes 30 to 30 of the second raw material activation-supply unit 16. 0.3 sccm of trimethylaluminum vapor held at 0 ° C. was introduced together with N ₂ carrier gas at 100 sccm. At this time, the pressure in the reactor 12 measured by a Baratron vacuum gauge was 0.3 Torr.
Met.

When film formation was carried out for 1 hour and the film composition was measured by RBS, it was found that the Ga / Al ratio was 3.2: 1 and was equal to the introduced gas ratio. The Ga + Al / N ratio was 1.05, which was a stoichiometric ratio. (Embodiment 6) Using the semiconductor manufacturing apparatus 50 of FIG. 3 and the same substrate as in Embodiment 1, the substrate was evacuated and heated to 500 ° C. N
₂ Gas is the first raw material activation-gas introduction pipe 2 of the supply unit 14
From No. 6, 500 sccm was introduced into a quartz tube 24 having a diameter of 25 mm, a microwave of 2.45 GHz was set at an output of 300 W, matching was performed, and discharge was performed. The reflected wave at this time was 0W. Further, 800 sccm of N ₂ gas was introduced into the quartz tube 24 having a diameter of 25 mm from the gas introduction tube 26 of the second raw material activation-supply section 16 and discharged at a power of 200 W with a microwave of 2.45 GHz. The reflected wave is 0W
Met. The substrate temperature was 600 ° C. First in this state
The trimethylgallium vapor held at room temperature was introduced at 1 sccm from the gas introduction pipe 30 of the raw material activation-supply unit 14 of the second raw material activation-supply unit 16 and the trimethylgallium held at 30 ° C. Indium vapor 1.0
20 sccm was introduced together with sccm and N ₂ carrier gas. Reactor 72 measured with a Baratron vacuum gauge at this time
The internal pressure was 0.2 Torr.

First, after depositing GaN for 1 minute in the first space 56, the substrate and the substrate holder 6 are provided on the second space 58 side.
2 and the heater 64 were moved, and InN was formed into a film for 1 minute. This operation was repeated 10 times to produce a multilayer film consisting of 20 layers. The time required for the movement of the substrate was about 2 seconds, and the emission state of the remote plasma did not change significantly before and after the movement. The composition of this film and the distribution in the film thickness direction are expressed as X
As a result of measurement with PS, RBS and secondary ion mass spectrometer,
It was found that GaN and InN having a substantially stoichiometric ratio were divided into layers of 10 nm each, and the boundary was clear.

[0048]

Since the present invention has the above-mentioned structure, it is possible to produce a high-quality and highly-functional semiconductor and semiconductor element in a short time with high productivity.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a semiconductor manufacturing apparatus according to a first embodiment of the present invention.

FIG. 2 is a schematic configuration diagram of a semiconductor manufacturing apparatus according to a second embodiment of the present invention.

FIG. 3 is a schematic configuration diagram of a semiconductor manufacturing apparatus according to a third embodiment of the present invention.

FIG. 4 is a schematic configuration diagram of a semiconductor manufacturing apparatus according to a fourth embodiment of the present invention.

[Explanation of symbols]

10 Semiconductor manufacturing equipment 12 reactor 18 Exhaust pipe 20 Substrate holder (heating and holding means) 22 Heater (heating and holding means) 24 quartz tube 26 Gas introduction pipe 28 microwave waveguide 30 gas introduction pipe 40 Semiconductor manufacturing equipment 44 high frequency coil 50 Semiconductor Manufacturing Equipment 52 reactor 54 partitions 60 exhaust pipe 62 Substrate holder (heating and holding means) 64 heater (heating and holding means) 70 Semiconductor manufacturing equipment 72 reactor 74 Exhaust pipe 76 bulkhead 90 Heater (heating and holding means) 92 Substrate holder (heating and holding means)

Claims (11)

(57) [Claims] 1. A group III element as a source of a group V element in a plasma state
A first reaction step of reacting an organometallic compound containing: and a step of reacting an auxiliary material with the product produced by the reaction.
And a semiconductor compound containing the group V element and the group III element.
A method of manufacturing a semiconductor, comprising: a film forming step of forming the film on a substrate . 2. A first plasma generation step of bringing a group V element source containing a group V element into a plasma state, and a plasma state by the first plasma generation step .
Adding an organometallic compound containing a group III element to a group V element,
Generate a reaction product composed of the group V element and the group III element
Process, a second plasma generating step for bringing the auxiliary material for preventing film defects into a plasma state, and the auxiliary material in the plasma state is generated by the reaction step.
A film forming step of forming a semiconductor compound containing a group V element and a group III element on a substrate by adding the above-mentioned product to the product . 3. A first plasma generating step for bringing a group V element source containing a group V element into a plasma state, and the plasma generated in the first plasma generating step, II
First addition of gaseous organometallic compounds containing Group I elements
And a step of adding the second plasma generation step of bringing the group V element source into a plasma state separately from the first plasma generation step and the plasma generated in the second plasma generation step It is used in the second addition step of adding a gaseous organometallic compound containing a group III element different from the group element, and the group III element added in the first addition step and the first plasma generation step. And a semiconductor compound containing the Group V element and the II added in the second adding step.
A method of manufacturing a semiconductor, comprising: a film forming step of forming, on a substrate, a mixed crystal of a group I element and a semiconductor compound containing the group V element used in the second plasma generation step. 4. The method for producing a semiconductor according to claim 1, wherein a gaseous raw material for controlling pn is further added in the second reaction step. 5. In the film forming step, for pn control
A further feature of adding a gaseous raw material.
2. The method for manufacturing a semiconductor according to 2. 6. The method for producing a semiconductor according to claim 3 , wherein a gaseous raw material for pn control is further added in at least one of the first addition step and the second addition step. . 7. A plasma generated from claim 1, characterized by using a high-frequency discharge and / or microwave discharge
5. The method for manufacturing a semiconductor according to any one of 5 above. 8. The semiconductor manufacturing method according to any one of claims 1 6, wherein the pre-Symbol V element is nitrogen. 9. A reactor for forming a semiconductor film on a substrate, a heating and holding means provided in the reactor for holding and heating the substrate, and a first supply for supplying a group V element source. means and, contiguous with said first supply hand Dan及 beauty said reactor, a first plasma generation means you the supplied group V element source in a plasma state, before Symbol of the first plasma generating means Group III element on the reactor side
Second supply means for supplying an organometallic compound containing element and first gas for supplying a plasma state
The third supply means and the third supply means and the reactor are connected and supplied continuously.
Second plasma generation that turns the first gas into a plasma state
Means and a second gas generator on the reactor side of the second plasma generating means.
And a fourth supply means for supplying a nitride semiconductor. 10. A method for forming a semiconductor film on a substrate
A reactor, partition means for partitioning the interior of the reactor, and a reactor provided inside the reactor for holding and heating the substrate.
The heating and holding means and the heating and holding means are partitioned by the partitioning means.
Move the heating and holding means so that it passes through all of the space.
Means for moving and a first gas for supplying a first gas for making a plasma state
A plurality of first supply means, each of the first supply means and the reactor are connected in succession.
Plural plasmas for converting the supplied first gas into a plasma state
Means for generating a plasma, and a second side for each of the plurality of plasma generating means on the side of the reactor.
A plurality of second supply means for supplying two raw material gases , and a space partitioned by the partition means.
Each is connected to at least one plasma generating means.
Semiconductor manufacturing equipment. 11. The semiconductor manufacturing apparatus according to claim 10 , further comprising exhaust means continuous to all of the spaces partitioned by the partition means.