JPH08222581A - Manufacture of semiconductor and semiconductor element - Google Patents

Abstract

PURPOSE: To provide the manufacture of a II-VI compound semiconductor film which shows n-type conductivity. CONSTITUTION: Using ZnF2 as the material of a heating evaporation source, an n-type ZnSSe clad layer 9-1 where fluorine is added and an n-type ZnSe light guide layer 9-2 are grown on an n-type GaAs substrate 8 by a molecular beam epitaxy method. Since chemical seeds including fluorine are supplied onto the substrate, a II-VI compound semiconductor film high in carrier density and low in resistivity and excellent in weatherability can be made with excellent controllability and reproductivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor, a semiconductor device and a method for manufacturing the same, and more particularly to a II-VI group compound semiconductor thin film exhibiting n-type conduction, a semiconductor light emitting element made of a II-VI compound semiconductor, and a manufacturing method thereof. It is about the method.

[0002]

2. Description of the Related Art As conventional technology, for example, conventional II
-Group VI semiconductor devices are, for example, Japanese Journal of Applied Physics, Vol. 31, L1478 (1992) (Japanese Journal of Applied Physic
s vol.31 pp.L1478 (1992)) or the Japanese Journal of Applied Physics, Volume 21 L3
Page 87 (1982) (Japanese Journal of Applied
Physics vol.21 pp.L387 (1982)), a method of obtaining an n-type II-VI group compound semiconductor by adding chlorine or gallium as an impurity to a II-VI group compound is used. (Japanese Patent Laid-Open No. 59-39798)
Japanese Patent Laid-Open No. 62-271438).

[0003]

[Problems to be solved by the invention] II-VI with chlorine added
As the group compound semiconductor, an n-type semiconductor with low resistance can be obtained, and one with high carrier density can be obtained, but the water resistance and weather resistance are low,
There was a problem that it is eroded relatively easily in a high humidity atmosphere.

Therefore, the element using the n-type II-VI group compound semiconductor to which chlorine is added has low weather resistance, and particularly in the case of a semiconductor laser which becomes unstable when the smoothness of the cleaved surface is lost, A device with a long life could not be obtained.

Further, in the II-VI group compound to which gallium is added, the carrier density of the obtained n-type semiconductor is low and the resistivity is also high, so that a highly efficient device cannot be obtained.

Further, in the molecular beam epitaxy (MBE) method, zinc chloride (Z
Since nCl ₂ ) has a high vapor pressure, it is necessary to lower the temperature of the raw material cell, so the controllability and reproducibility of the addition amount are low, and it is likely to cause contamination of the MBE equipment during baking. There was a problem.

It is an object of the present invention to solve the above-mentioned drawbacks and to provide a method for producing an n-type II-VI group compound semiconductor having high carrier density, low resistance and high weatherability with good controllability and reproducibility. To do. Another object of the present invention is to provide a semiconductor laser having high efficiency and high weather resistance and long life, and a method for manufacturing the same.

[0008]

In order to achieve this object, a method for producing a semiconductor according to the present invention is a method for producing a semiconductor in which a II-VI group compound semiconductor thin film is formed on a substrate by a molecular beam epitaxy method. It is characterized by supplying a chemical species containing fluorine to the above.

The semiconductor manufacturing method of the present invention is the semiconductor manufacturing method of forming a II-VI group compound semiconductor thin film on a substrate by a metal organic chemical vapor deposition method, wherein the II-VI group compound semiconductor thin film forming atmosphere is used. Is characterized in that a chemical species containing fluorine is introduced into the above.

The semiconductor device of the present invention is characterized in that it is made of p-type and n-type II-VI group compound semiconductors, and the n-type semiconductor region is made of a fluorine-added II-VI group compound semiconductor. To do.

Further, the method for producing a semiconductor device of the present invention is the method for producing a semiconductor device, wherein the II-VI group compound semiconductor laminated film is formed on the substrate by a molecular beam epitaxy method or a metal organic chemical vapor deposition method. It is characterized by including an n-type semiconductor region forming step of supplying a chemical species containing fluorine.

[0012]

The function of this technical means is as follows.

That is, in a method for producing a semiconductor in which a II-VI group compound semiconductor thin film is formed on a substrate by a molecular beam epitaxy method, a fluorine-containing chemical species is supplied to the substrate to easily increase the amount of fluorine atoms. A high quality II-VI group compound semiconductor crystal thin film added at a high concentration can be prepared.

Further, a low resistance p-type II-VI group compound semiconductor layer can be continuously and easily produced, and a semiconductor device having a pn junction can be produced.

Further, compared to the vapor pressure of zinc chloride, which is a raw material when chlorine is added in the MBE method, a raw material having a low vapor pressure can be used as a raw material for adding fluorine, so that controllability during semiconductor thin film production can be achieved. -It can improve reproducibility and reduce device contamination.

Further, metal organic chemical vapor deposition (MOCVD)
In the method of manufacturing a semiconductor, wherein a II-VI group compound semiconductor thin film is formed on a substrate by supplying a chemical species containing fluorine onto the substrate, a high-quality II-containing fluorine atom easily added at a high concentration. A Group VI compound semiconductor crystal thin film can be produced. As a result, an n-type II-VI compound semiconductor having a large area and a uniform film quality can be manufactured at low cost, and the formation temperature of the II-VI compound semiconductor can be increased. A Group VI compound semiconductor thin film can be manufactured.

Fluorine added to the II-VI group compound substitutes for the VI group element position in the compound crystal to supply free electrons. Further, since the fluorine atom has high reactivity and the bonding strength with the zinc atom is high, the doping amount can be easily increased. As a result, the II-VI group compound semiconductor thin film to which fluorine is added exhibits n-type conductivity with high carrier density and low resistance.

Since the bond between the chlorine atom and the group II metal atom is weak and the reactivity with water molecules is high, the addition of chlorine II
-Group VI compound semiconductors were easily eroded in a high humidity atmosphere and had low water resistance and weather resistance. But with the fluorine atom
Since the bonds between the group II metal atoms are strong and the reactivity with water molecules is low, the II-VI group compound semiconductor containing fluorine is not easily corroded even in a high humidity atmosphere, and has excellent water resistance and weather resistance. ing.

With the above operation, according to the method for producing a semiconductor of the present invention, in the method for producing a semiconductor in which the II-VI group compound semiconductor thin film is formed on the substrate by the molecular beam epitaxy method, fluorine is added on the substrate. By supplying the contained chemical species, an n-type II-VI group compound semiconductor thin film having high carrier density, low resistivity and excellent weather resistance can be manufactured with good controllability and reproducibility.

Further, on the substrate by the metal organic chemical vapor deposition method
In a method of manufacturing a semiconductor for forming a II-VI group compound semiconductor thin film, by introducing a chemical species containing fluorine into the II-VI group compound semiconductor thin film forming atmosphere, high carrier density, low resistivity, and weather resistance. N-type II-VI with excellent properties
A group compound semiconductor thin film can be manufactured.

Further, by using this principle, it is possible to provide a semiconductor element having excellent water resistance and weather resistance.

[0022]

EXAMPLE A semiconductor manufacturing method and a semiconductor device according to the present invention have high carrier density, low resistance, and excellent weather resistance.
Since a type II-VI group compound semiconductor thin film can be provided, it is useful as a light emitting element such as a light emitting diode and a semiconductor laser, a light receiving element, a non-linear optical element, and the like. Further, the semiconductor element of the present invention is II-VI which is highly efficient and has excellent water resistance and weather resistance.
Since it is a group compound semiconductor element, it is useful as a semiconductor laser element for high-density information recording devices, image display devices, information communication, and the like.

The II-VI group compounds of the present invention include Zn,
At least one group II element selected from Cd, Hg, Be, Mg, Ca, and Sr, and at least one selected from S, Se, and Te
It is preferable to use a compound or mixed crystal composed of a Group VI element. II-V obtained by selecting from the above elements
Group I compounds are suitable as constituent materials for short-wavelength semiconductor lasers because they can greatly change the lattice constant and the size of the band gap and can easily form a low resistance film by adding p-type impurities.

The fluorine-containing molecule of the present invention is ZnF ₂ ,
_{NH 4 HF 2, S n F} m, Se n F m (n = 1~2, m = 1~
10), F ₂ , HF, or a molecule produced by heating or exciting the molecule, II
-VI without reducing the crystallinity of group VI compound semiconductor thin film
A large amount of fluorine atoms can be efficiently added to the position of the group element.

Example 1 An example of manufacturing an n-type ZnSe compound semiconductor on a GaAs substrate will be taken up below and a specific example will be described in detail.

First, as shown in FIG. 1, heating evaporation sources 4 to 6 of a molecular beam epitaxy (MBE) apparatus 1 were loaded with high-purity Zn, Se, and ZnF ₂ as raw materials. Further, a GaAs single crystal substrate 3 having a (100) plane whose surface was cleaned was attached to the substrate heating mechanism 2.

Next, the vacuum container of the MBE apparatus 1 is set to 10 ^-9.
It was evacuated to an ultra-high vacuum of about Torr or less. afterwards,
Each heating evaporation source 4-6 was heated so that an appropriate molecular beam intensity could be obtained. In this case, for example, the molecular beam intensity of Zn and the molecular beam intensity of Se are substantially the same.

The intensity of the Zn molecular beam is preferably 1 × 10 ⁷ times or less that of the ZnF ₂ molecular beam.
When it is 1 × 10 ⁷ times or more, the addition density of fluorine is insufficient, and the obtained fluorine-added ZnSe thin film has high resistivity and low carrier concentration, which is not desirable as an n-type semiconductor.

When chlorine was added, it was necessary to maintain the temperature of the heating evaporation source of zinc chloride as a raw material at a low temperature of 150 to 300 ° C., while the temperature of the heating evaporation source of zinc fluoride was Since an appropriate molecular beam intensity could be obtained at a high temperature of 400 ° C. or higher, the controllability and reproducibility of ZnSe thin film production could be improved, and the contamination of the device could be reduced.

Next, the substrate 3 was heated to about 600 ° C. to further clean the surface. After that, the substrate 3 was cooled to a temperature suitable for crystal growth. This substrate temperature is 200 ℃ to 40 ℃
0 ° C is suitable. When the substrate temperature is 200 ° C. or lower, Zn and Se are very likely to adhere to each other, so that a portion having a high density of Zn and Se is formed, resulting in poor crystallinity. Further, when the substrate temperature is 400 ° C. or higher, the crystallinity is poor because Zn and Se are re-evaporated from the obtained crystal.

ZnSe produced by the above method
The thin film shows n-type conduction when Hall measurement is performed, and it is 5 × 10 5.
A high carrier density of ¹⁸ cm ⁻³ was obtained and a low resistivity of 5 × 10 ⁻³ Ω · cm was exhibited. This indicates that fluorine is incorporated at the selenium position in the crystal and effectively acts as a donor. It is also possible to further increase the carrier density by increasing the cell temperature of ZnF ₂ .

Further, F ₂ gas is caused to flow by using an RF plasma gun instead of the ZnF ₂ raw material cell, and F ₂ molecules and atomic fluorine excited by RF plasma are supplied during the growth of ZnSe to obtain 8 ×. A high carrier density of 10 ¹⁸ cm ^-3 was obtained, and an n-type ZnSe thin film having a low resistance of 3 × 10 ^-3 Ωcm was formed.

ZnSe to which chlorine was added at 5 × 10 ¹⁸ cm ^-3
After leaving the thin film in the air of 100% humidity at room temperature for 48 hours and observing its surface condition, the Z
It was observed that the surface of the nSe thin film was eroded and partially deliquesced to generate minute water droplets. Furthermore, the ZnSe thin film left in a high humidity atmosphere for 2 to 7 days was organically washed with methanol and acetone, and the surface was observed to be 100Å
From 1 to 1000 Å was generated.

On the other hand, when the ZnSe thin film containing fluorine having the same carrier density and prepared by the above method was left under the same conditions, no change was observed in the surface state,
The surface condition of the clean mirror surface was maintained.

Further, with the ZnSe thin film added with gallium produced by the same method, a thin film having a carrier density of 3 × 10 ¹⁶ cm ^-3 or more could not be produced.

As described above, by using the semiconductor manufacturing method of the present invention, high carrier density and low resistivity
Moreover, an n-type II-VI group compound semiconductor thin film excellent in water resistance and weather resistance could be manufactured with good controllability and reproducibility.

In this example, ZnSe thin films were prepared using Zn and Se as main raw materials, but the same results were obtained by growth by MBE or MOCVD using ZnSe compounds as raw materials.

In this embodiment, fluorine-containing ZnSe is used.
The method for producing a thin film has been described.
Other II-VI group compound crystals such as nS and ZnTe, and ZnS
Se, ZnCdSe, ZnMgSSe, ZnHgSSe
Similar improvements in water resistance and weather resistance were also observed for the II-VI group compound mixed crystals.

Furthermore, in this embodiment, ZnF ₂ and F ₂ molecules were used as the fluorine feed material, but ZnF ₂ and NH ₄ HF were used.
_{2, S n F m, Se} n F m (n = 1~2, m = 1~10),
The same applies to HF.

(Example 2) Next, an example of a blue semiconductor laser having a separate confinement type hetero structure (SQW-SCH structure) having a single quantum well will be taken up and a specific example will be described. It is sectional drawing which shows the structure of a semiconductor laser typically. As a method of forming this structure, a molecular beam epitaxy (MBE) growth method is preferable because a p-type conductive layer can be easily formed. ZnSe for the substrate
A GaAs single crystal substrate 8 having a lattice constant relatively close to is used. As the GaAs single crystal substrate 8, a low resistance n type substrate was used so that the electrode could be removed from the substrate. In addition, the temperature of the substrate is 29 in order to obtain a II-VI group compound semiconductor with good crystallinity.
It was set to 0 ° C.

First, by irradiating a molecular beam of zinc-fluoride (ZnF ₂ ) as a donor source onto the substrate at the same time as a molecular beam of metallic zinc, metallic selenium, and zinc sulfide, which are crystal host materials, in an ultrahigh vacuum. An n-type region 9-1 was formed by adding fluorine to a ZnS _0.07 Se _0.93 clad layer having a thickness of 1 μm.

Here, the cladding layer is made of ZnS _0.07 Se.
_{The 0.93} mixed crystal was used to suppress the occurrence of structural defects due to lattice misalignment by lattice matching with the substrate during growth, and to obtain a layer with good crystallinity. Zn on GaAs substrate
In the case of the SSe mixed crystal, the S composition is lattice-matched at 0.06 at room temperature, and is 0.0 at 400 ° C. which is the highest temperature used in the normal epi growth method for forming a double hetero structure.
Because of lattice matching at 9, a film with good crystallinity can be obtained in this composition region.

The thickness of the n-type region 9-1 of the ZnS _0.07 Se _0.93 cladding layer is 1 μm, but it is 0.5 μm.
If it is m or more, the influence of the substrate can be ignored.

Next, by stopping the molecular beam of zinc sulfide and irradiating the molecular beam of metallic zinc, metallic selenium and zinc fluoride onto the substrate, the n-type region of the 0.2 μm thick ZnSe optical guide layer by the addition of fluorine. 9-2 was formed.

Next, the molecular beam of zinc fluoride is stopped, a molecular beam of metal cadmium is newly added, and irradiation is performed with the molecular beam of metal zinc and metal selenium to form an active region 1.
A Zn _0.8 Cd _0.2 Se active layer 3 having a thickness of 00Å was formed.

Next, by stopping the molecular beam of metal cadmium and irradiating it with the molecular beam of active nitrogen in addition to the molecular beams of metal zinc and selenium, the nitrogen-added p-type of the ZnSe optical guide layer with a thickness of 0.2 μm is formed. Region 11-1 was formed.

Next, by irradiating with a molecular beam of zinc sulfide, the nitrogen addition p of the ZnS _0.07 Se _0.93 cladding layer is increased.
The mold region 11-2 was formed to 0.5 μm.

Here, n-type and p-type ZnSe and Z
The carrier density of the nSSe thin film is preferably 5 × 10 ¹⁶ cm ⁻³ or more at room temperature in order to obtain sufficient electric conduction.

Next, in order to reduce the contact resistance of the p-type electrode,
By stopping the molecular beam of zinc sulfide and further increasing the molecular beam intensity of active nitrogen, 1000 Å of p ⁺ type ZnSe contact layer 12 having an acceptor concentration of 1 × 10 ¹⁸ cm ⁻³ or more was formed.

Further, a width of 5 μm is formed on the p ⁺ type ZnSe layer 5.
An insulator (SiO2) layer 13 having stripe-shaped grooves was prepared, and an Au electrode layer 14 was vapor-deposited. In addition, n-type GaA
The In electrode layer 7 was vapor-deposited on the back surface of the substrate 1.

Finally, the resonator was cleaved so as to have a length of about 500 μm in each length and width, and a cleaved surface mirror was formed on the end face to form a resonator.

The semiconductor laser device 15 thus obtained oscillated at a wavelength of 512 to 517 nm, and the oscillation threshold current was between 96 mA and 110 mA. Further, the operating voltage during oscillation was between 21.1 V and 21.5 V, which showed high reproducibility.

Under the same growth conditions, a device having an n-type conductive layer obtained by filling a zinc chloride raw material instead of the zinc fluoride raw material and adding chlorine according to the prior art was also prepared. The element to which chlorine was added also oscillated at a wavelength of 513 to 519 nm, and the oscillation threshold current was between 99 mA and 117 mA. However, the amount of chlorine added during the growth of the n-type conductive layer fluctuates, so operation during oscillation The voltage had a variation from 21V to 37V.

As a result of leaving the semiconductor laser device in the atmosphere for one month, the oscillation threshold current of the device having an n-type conductive layer by chlorine addition according to the prior art was increased to 300 mA or more, whereas by the addition of fluorine according to the present invention. The oscillation threshold currents of the devices having the n-type conductive layer were all 120 mA or less, and improvement in weather resistance was observed.

Further, a device having an n-type conductive layer by adding chlorine according to the conventional technique is used at room temperature in air with a humidity of 100%.
When the end face was observed after standing for a period of time, it was observed that water in the atmosphere eroded the concave surface of the n-type conductive layer and partially generated deliquescent water droplets, but left the same conditions. No change was observed on the end face of the device having the n-type conductive layer by the addition of fluorine according to the present invention.

As described above, according to the semiconductor element having the n-type II-VI group compound semiconductor layer by the addition of fluorine of the present invention,
It was found that the weather resistance and water resistance of the semiconductor element can be improved and the element operating voltage is also excellent in reproducibility.

Although nitrogen was used as the dopant for the p-type layer here, phosphorus, arsenic, lithium, or sodium can be used instead.

In this embodiment, II-V having a laser structure is also used.
Although the usual MBE method is used as a growth method for a group I compound semiconductor multilayer film, the MBE method or MOC method using a compound as a raw material.
The same effect can be obtained by the VD method.

Although ZnF ₂ was used as the fluorine feed material in this embodiment, NH ₄ HF ₂ , S _n F _m , and Se _n F _{m are used.}
(N = 1 to 2, m = 1 to 10), F ₂ , HF, or a chemical species generated by heating or exciting the molecule can be similarly applied.

In this embodiment, the substrate is n-type Ga.
Although As is used, when n-type ZnSe is used, or when the structure is completely opposite in electrical conductivity to the above, that is, p
Similar effects can be obtained by forming an element with a structure in which the n-type and the n-type are interchanged.

In this embodiment, ZnSS is used as the cladding layer.
Although ZnSe is used for the waveguide layer and ZnCdSe for the active layer, ZnMgSSe is used for the cladding layer, ZnSSe is used for the waveguide layer, and ZnSe or Zn is used for the active layer.
The same effect can be obtained by the present invention also in a semiconductor laser using CdSe.

In this embodiment, a single quantum well composed of one ZnCdSe layer is used as the active region, but a plurality of ZnXCd1-XSe (0.1≤X≤0.4) quantum well layers and at least one or more layers are used. ZnSySe1-Y (0 ≦ Y ≦ 0.1)
Similar results were obtained using a multi-quantum well structure composed of barrier layers.

In this embodiment, the contact layer is made of p.
^{Although a +} type ZnSe layer is used, a p ⁺ ZnTe layer or p ⁺
A ZnTe / ZnSe multilayer film and ap ⁺ ZnHgSe layer can be used as the contact layer. Further, although the Au electrode is used in this embodiment, an Au / Pd electrode or a Pt electrode can be used.

In this embodiment, II is directly formed on the GaAs substrate.
Although the -VI group compound semiconductor layer is grown, the crystallinity of the II-VI group compound semiconductor layer can be improved by growing the GaAs buffer layer before the growth of the II-VI group compound semiconductor layer.

Further, although the semiconductor laser of the electrode stripe structure is taken up in the present embodiment, the present invention can be applied to the semiconductor laser device of other structures such as a buried structure and a structure by ion implantation.

[0066]

As described above, the present invention is a method for producing a semiconductor in which a II-VI group compound semiconductor thin film is formed on a substrate by a molecular beam epitaxy method, and a chemical species containing fluorine is supplied onto the substrate. Since it is a semiconductor manufacturing method characterized by that, it is possible to manufacture an n-type II-VI group compound semiconductor thin film having high carrier density, low resistivity, and excellent weather resistance with good controllability and reproducibility. There is.

Further, the present invention provides a method for producing a semiconductor in which a II-VI group compound semiconductor thin film is formed on a substrate by a metal organic chemical vapor deposition method, wherein fluorine is added to the II-VI group compound semiconductor thin film forming atmosphere. Since it is a method for producing a semiconductor, which is characterized by introducing a chemical species containing therein, it is possible to produce an n-type II-VI group compound semiconductor thin film having high carrier density, low resistivity and excellent weather resistance. There is.

Further, the present invention is a semiconductor device characterized by being made of a II-VI group compound semiconductor, and the n-type semiconductor region being made of a fluorine-added II-VI group compound semiconductor. There is an effect that a II-VI group compound semiconductor device having excellent weather resistance can be provided.

Further, the present invention is a method for producing a semiconductor device in which a II-VI group compound semiconductor laminated film is formed on a substrate by a molecular beam epitaxy method or a metal organic chemical vapor deposition method, in which a chemical compound containing fluorine is provided on the substrate. A method of manufacturing a semiconductor device characterized by including an n-type semiconductor region forming step of supplying seeds, so that the controllability and reproducibility of the device manufacturing are improved, and the II-VI group is excellent in water resistance and weather resistance. There is an effect that a compound semiconductor device can be provided.

[Brief description of drawings]

FIG. 1 is a molecular beam epitaxy (MB) of Example 1 of the present invention.
E) Schematic diagram of the device

FIG. 2 is a sectional view of a II-VI group compound semiconductor laser device of Example 2 of the present invention.

[Explanation of symbols]

1 molecular beam epitaxy (MBE) device 2 substrate heating mechanism 3 GaAs substrate 4 heating evaporation source containing Zn 5 heating evaporation source containing Se 6 heating evaporation source containing ZnF ₂ 7 In electrode 8 n-type GaAs substrate 9 fluorine N-type conductive layer by addition 9-1 n-type ZnSSe: F clad layer 9-2 n-type ZnSe: F light guide layer 10 ZnCdSe active layer 11 p-type conductive layer by nitrogen addition 11-1 p-type ZnSe: N light guide layer 11-2 p-type ZnSSe: N clad layer 12 p ⁺ type ZnSe: N contact layer 13 SiO ₂ insulating layer 14 Au electrode 15 semiconductor laser device

Claims (11)

[Claims] 1. II-V on a substrate by molecular beam epitaxy
A method for producing a semiconductor for forming a Group I compound semiconductor thin film, comprising supplying a chemical species containing fluorine onto the substrate. 2. II-VI on a substrate by metalorganic vapor phase epitaxy
A method for producing a semiconductor for forming a group compound semiconductor thin film, comprising introducing a chemical species containing fluorine into the atmosphere for forming the group II-VI compound semiconductor thin film. 3. A semiconductor device comprising a II-VI group compound semiconductor, wherein the n-type semiconductor region is formed of a fluorine-added II-VI group compound semiconductor. 4. A method of manufacturing a semiconductor device, wherein a II-VI group compound semiconductor laminated film is formed on a substrate by a molecular beam epitaxy method or a metal organic chemical vapor deposition method, wherein a chemical species containing fluorine is supplied onto the substrate. A method of manufacturing a semiconductor device, comprising the step of forming an n-type semiconductor region. 5. Group II element is Zn, Cd, Hg, Be, M
3. The method for producing a semiconductor according to claim 1, wherein the semiconductor element is at least one of g, Ca, and Sr, and the group VI element is at least one of S, Se, and Te. 6. Group II element is Zn, Cd, Hg, Be, M
4. The semiconductor device according to claim 3, wherein the semiconductor element is at least one of g, Ca, and Sr, and the group VI element is at least one of S, Se, and Te. 7. Group II element is Zn, Cd, Hg, Be, M
5. The method of manufacturing a semiconductor device according to claim 4, wherein at least one of g, Ca, and Sr, and the group VI element is at least one of S, Se, and Te. 8. A chemical species containing fluorine is ZnF ₂ , NH ₄ HF.
_{2, S n F m, Se} n F m (n = 1~2, m = 1~10),
_3. F ₂ or HF or a chemical species produced by heating the molecule.
A method for manufacturing a semiconductor according to. 9. A chemical species containing fluorine is ZnF ₂ , NH ₄ HF.
_{2, S n F m, Se} n F m (n = 1~2, m = 1~10),
The method of manufacturing a semiconductor device according to claim 4, wherein F ₂ , HF, or a chemical species generated by heating the molecule is used. 10. The chemical species containing fluorine is a fluorine atom or
Is ZnF₂, NH_FourHF ₂, S_nF_m, Se_nF_m(N = 1 to 1
2, m = 1 to 10), F₂To excite HF molecules
A chemical species produced by
Or the method of manufacturing a semiconductor according to 2. 11. The chemical species containing fluorine is a fluorine atom or
Is ZnF₂, NH_FourHF ₂, S_nF_m, Se_nF_m(N = 1 to 1
2, m = 1 to 10), F₂To excite HF molecules
5. The chemical species generated by
A method of manufacturing a semiconductor device according to item 1.