JP2692804B2 - Method of forming crystalline deposited film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]   The present invention relates to a method for forming a crystalline deposited film, and particularly to a deposition method.
Utilizing the difference in the nucleation density of the deposited material depending on the type of surface material
Deposition of single crystals or polycrystals with controlled grain size
The present invention relates to a method for forming a film.   The present invention relates to a semiconductor integrated circuit, an optical integrated circuit,
Circuits, electronic elements, optical elements, magnetic elements, piezoelectric elements, or
Crystallinity of single crystal and polycrystal used for surface acoustic devices
Applies to the formation of deposited films. [Prior art and its problems]   Conventionally, single crystals used for semiconductor electronic devices, optical devices, etc.
Thin films are grown epitaxially on single-crystal substrates.
Had been formed. For example, a silicon single crystal substrate (silicon wafer)
C) On top, Si, Ge, GaAs, etc. are deposited from liquid phase, gas phase or solid phase.
It is known that it grows by epitaxial growth.
Single crystals such as GaAs and GaAlAs are grown on the crystal substrate.
Is known to grow. Formed in this way
Semiconductor devices and integrated circuits,
Light emitting elements such as semiconductor lasers and LEDs are manufactured.   Recently, ultra-high-speed transistors using two-dimensional electron gas
Research and development of superlattice devices using quantum wells and quantum wells
However, what made these possible, for example, ultra-high vacuum
MBE (Molecular Beam Epitaxy) and MOCVD (Organic Metal
High-precision epitaxy technology such as chemical vapor deposition.   In such epitaxial growth on a single crystal substrate,
A lattice is placed between the monocrystalline material of the plate and the epitaxial growth layer.
It is necessary to match the constant with the coefficient of thermal expansion. For example
A Si single crystal thin film is formed on the edge single crystal substrate
Although it is possible to grow it epitaxially, the lattice constant of
Components of crystal lattice defects and sapphire at the interface due to misalignment
The diffusion of aluminum into the epitaxial layer is
This is a problem in application to child elements and circuits.   Thus, the conventional single crystal thin film grown by epitaxial growth
It is clear that the method of forming the film greatly depends on the substrate material.
You. Mathews et al. Discuss substrate materials and epitaxial growth layers.
Are examining the combination of (EPITAXIAL GROWTH.Academic Pr
ess, New York, 1975 ed.by J.W. Mathews).   The size of the substrate is currently about 6 inches for a Si wafer.
Therefore, the size increase of GaAs and sapphire substrates has been delayed.
You. In addition, single-crystal substrates have high manufacturing costs,
The cost per tip increases.   Thus, a high-quality device is manufactured by the conventional method.
To form a possible single crystal layer, the type of substrate material must be extremely
In a narrow range.   On the other hand, semiconductor elements are stacked in the normal direction of the
Research on three-dimensional integrated circuits that achieve integration and multifunctionality
Development has been active in recent years, and on inexpensive glass
Switches of solar cells and liquid crystal pixels in which elements are arranged in an array
Research and development of large-area semiconductor devices such as
It is becoming popular every year.   What is common to both of these is that semiconductor thin films can be made amorphous.
It is formed on an edge, and electronic elements such as transistors are formed there.
It is necessary to have the technology to produce. Among the,
Technology for forming high-quality single-crystal semiconductor on amorphous insulator
Is desired.   Generally, SiO_TwoOf thin film on amorphous insulator substrate
The deposited film due to the lack of long-range order of the substrate material.
The crystal structure of is amorphous or polycrystalline. Amorphous film here
Means that the short-range order of the closest atom is preserved,
There is no longer-range order than this, and the polycrystalline film
Is a single crystal grain that does not have a specific crystal orientation and is isolated at the grain boundary.
It has been assembled and assembled.   For example, SiO_TwoWhen Si is formed on top by CVD method,
If the deposition temperature is about 600 ° C or less, amorphous silicon
If the temperature is higher than this, the particle size will be in the range of hundreds to thousands Å
It becomes distributed polycrystalline silicon. However, polycrystalline silicon
Particle size and its distribution vary greatly depending on the forming method
You.   In addition, amorphous or polycrystalline films can be lasered or bar-shaped heaters.
By melting and solidifying with an energy beam such as
Therefore, a large number of particles with a large particle size on the order of microns or millimeters
Crystal thin film has been obtained (Single-Crystal silicon on n
on-single-crystal insulators, Journal of crystal
Growth vol, 63, No.3, October, 1983 edited by G.W.Cull
en).   The thin film of each crystal structure formed in this way is
Form a transistor and measure electron mobility from its characteristics
And 0.1 cm for amorphous silicon^Two/ V ・ sec, particle size of several hundred Å
1 to 10 cm for polycrystalline silicon with^Two/ V ・ sec, molten solid
Of polycrystalline silicon with large grain size
The same mobility as in the case is obtained.   From this result, it was found that the element formed in the single crystal region in the crystal grain
The element formed over the grain boundary
It can be seen that there is a great difference in the dynamic characteristics. That is,
The deposited film on the amorphous obtained by the method is amorphous or has a grain size.
A device with a polycrystalline structure with a distribution and created there
Has higher performance than devices fabricated in a single crystal layer.
It will be inferior. Because of that, as a simple application
Limited to switching elements, solar cells, photoelectric conversion elements, etc.
You.   In addition, a polycrystalline thin film with a large grain size is formed by melting and solidification.
Is to apply an amorphous or single-crystal thin film to each wafer.
Since it is scanned with a gee-beam, it takes a lot of time to increase the particle size.
It is said that mass production is poor and it is not suitable for large area.
Had problems.   Furthermore, in recent years, research on diamond thin film growth has become active.
It is getting better. Diamond thin films are especially useful as semiconductors.
With a wide gap of 5.5 eV, the conventional semiconductor material S
Operates at a higher temperature (up to 500 ℃) than i, Ge, GaAs, etc.
it can. The carrier mobility is that of Si for both electrons and holes.
Is higher than (the electron is 1800 cm^Two/ V ・ sec, hole is 1600cm^Two
/ V ・ sec) and thermal conductivity is also very high. Because of this, fever
Promising application to high power consumption type semiconductor devices
Have been.   However, conventionally, diamond has been
Epitaxial growth of diamond thin film on Mondo substrate
There is a report (N. Fujimoto, T. Imai and A. Doi Pr
o.of Int.Couf.IPAT), on substrates other than diamond substrates
Reports of successful growth of heteroepitaxyal
No.   In general, using excitation by microwave, CH_Fourof
Thermal filament and electron beam irradiation using hydrocarbon gas
Generates diamond nuclei, but in general nuclei
The formation density is low and it is difficult to form a continuous thin film. Parable
Even if it becomes a continuous thin film, it has a polycrystalline structure with a large grain size distribution.
Therefore, there is difficulty in application to semiconductor devices.   Also, as long as a diamond substrate is used, it is naturally expensive and
However, there is also a problem in increasing the area, which is not suitable for practical use.   As described above, the conventional crystal growth method and
As a result, three-dimensional integration and larger area are
It is not easy, and practical application to devices is difficult.
Required to produce devices with excellent properties
Single crystal and polycrystal etc.
Could not be formed at cost.   On the other hand, conventionally, a functional film, especially a crystalline semiconductor film, has been required.
Individually suitable components from the viewpoint of desired physical properties and applications
A membrane method is employed.   For example, if necessary, a hydrogen atom (H) or a halogen atom
Amorphous or multi-electrons whose unpaired electrons are compensated by a compensating agent such as
Crystalline non-single crystal silicon [hereinafter referred to as "NON-Si (H, X)"
Abbreviations, especially when showing amorphous silicon
"A-Si (H, X)", when indicating polycrystalline silicon
Described as "poly-Si (H, X)". ] Silicon-based deposition of films
Membrane [In addition, microcrystalline silicon is commonly called A-Si (H, X)
It goes without saying that it is in the range. ] To form
Is a vacuum deposition method, plasma CVD method, thermal CVD method, thermal CVD method,
Reaction sputtering method, ion plating method, optical CV
The D method and the like have been tried, and the plasma CVD method is generally used.
Where it is optimally used and is being commercialized
It is.   However, the conventional generalized plasma CVD method
The reaction process in the formation of a silicon-based deposited film by
It is considerably more complicated than the conventional CVD method, and its reactor
There are many unknown points. Also, the formation parameter of the deposited film
Data, for example, the temperature of the substrate, the ratio of the flow rate of the introduced gas,
Pressure, high frequency power, electrode structure, reaction vessel structure, exhaust
Speed, plasma generation method, etc.
Due to the combination of
It becomes stable and has a significant adverse effect on the formed deposited film.
I often gave it. In addition, the device-specific
Parameters must be selected for each device,
However, it is difficult to generalize the manufacturing conditions.
It was a shape.   In addition, crystalline silicon-based deposition in plasma CVD
When forming a film, the component on which the film forming substrate is disposed is formed.
In the membrane space, high power high frequency or microwave
Electrons generated by the
And many ion species damage the film during the film formation process.
However, it causes deterioration of film quality and non-uniformity of film quality.
Or Moreover, the conditions for crystallization of the deposited film are narrow,
Therefore, a polycrystalline deposited film with stable characteristics can be produced.
Is said to be difficult.   Incidentally, silicon, germanium, II-VI and III
For forming an epitaxial deposited film such as a -V semiconductor,
Gas phase epitaxy and liquid phase epitaxy can be broadly divided
Used (generally a strict definition of epitaxy)
A single crystal with its single crystal axis aligned with the crystal axis
Is to grow crystals, but here epitaxy is broader.
Interpretation of taxi, growth on single crystal substrate
It is not limited. ).   Liquid phase epitaxy is a metal solvent that has been dissolved into a liquid.
Dissolve the raw materials for semiconductors into supersaturated state at high temperature,
Precipitates semiconductor crystals on the substrate by cooling the solution
It is a way to make it. According to this method, the crystals can be variously etched.
Created in the state of thermal equilibrium closest to that of pitaxy technology
Therefore, although crystals with high integrity can be obtained, mass productivity is poor.
Thin and uniform epitaxy due to poor surface condition
For optical devices that require a
Problems such as affecting the yield and device characteristics of
It is rarely used because it can be said.   On the other hand, vapor-phase epitaxy uses vacuum evaporation,
Physical method such as the metallization method or hydrogen reduction method of metal chlorides
For chemical methods such as thermal decomposition of organic metals or metal hydrides
Is being tried more. Above all, it is a kind of vacuum deposition method
S-line epitaxy is a dry process under ultra-high vacuum.
Therefore, the crystal can be highly purified and grown at low temperature.
It is said that the concentration controllability is good and a relatively flat deposited film can be obtained.
However, the film deposition equipment is very expensive.
In addition, the surface defect density is high, and the molecular beam fingers
Effective control of tropism is untapped, and also large area
It is difficult to commercialize and mass production is not so good.
Due to many problems, it has not been commercialized yet.
No.   Hydrogen reduction method of metal chloride or organic metal or metal water
In general, the method of thermal decomposition of the nitride
This is called the dry CVD method or MO-CVD method.
For these, a film forming apparatus can be manufactured relatively easily,
Metal chlorides, metal hydrides and organometals used
Whether high-purity products are easily available
Nowadays, it has been widely studied and its application to various devices has been examined.
Is being debated.   However, in these methods, the substrate temperature is reduced
Heating to a temperature higher than the temperature at which reaction or thermal decomposition reaction occurs
Which limits the choice of substrate material and
If the decomposition of the raw material is insufficient,
Contamination due to impurities is easily caused, and doping control
It has disadvantages such as poor properties. And also of the deposited film
Depending on the application, large area, uniform film thickness, film quality
Satisfies uniformity sufficiently and reproducibility by high-speed film formation
There is a demand for mass production with
Mass production while maintaining practical characteristics satisfying demands
The technology that makes it possible has not yet been established.
is there. 〔Purpose〕   A main object of the present invention is to solve the above conventional problems.
An object of the present invention is to provide a method for forming a crystalline deposition film. The present invention
The other purpose of the
Grain boundaries are not limited by the plate material, structure, size, etc.
Good quality such as single crystal not containing Cu and polycrystal with grain boundary constraint
To provide a method for forming the crystals of.   Still another object of the present invention is to use a simple
To provide a method for efficiently forming the above crystal in a simple process.
And there.   Still another object of the present invention is to achieve energy saving.
Sometimes it is easy to control the quality of the film, and the desired characteristics can be obtained over a large area.
A method for forming a deposited film that can obtain a semiconductive crystalline deposited film is proposed.
To provide.   Still another object of the present invention is to achieve excellent productivity and mass
High quality and excellent physical properties such as electrical, optical and semiconductor
A deposited film that can easily and efficiently form a crystalline deposited film
It is to provide a forming method. [Means for solving the problem]   A method for forming a crystalline deposited film of the present invention that achieves the above object
Is Si due to the activation space (A)_TwoF₆Activated species
(A) and H due to the activation space (B)_TwoActivated activity
Seed (B) and nuclide at a flow rate ratio of 10: 1 to 1:10 separately
Non-nucleated surface (S_NDS) And a single nucleus
The non-nucleating surface (S
_NDS) Nucleation density (ND_S) Higher nucleation density (N
D_L) Nucleation surface (S)_NDL) And adjacent to
Chemically by introducing it into the film-forming space where the substrate having a free surface is arranged.
By reacting, the nucleation surface (S_NDL)
To form a single nucleus in and to grow a single crystal from the nucleus
It is characterized by. [Action]   The method for forming a deposited film according to the present invention having the above-described structure includes forming a deposited film.
Plasma by applying discharge energy to the raw material gas
Instead of the conventional plasma-enhanced CVD method of forming a discharge, activated species
The deposited film can be formed without using plasma reaction.
One of the characteristics is that
No adverse effects due to etching or abnormal discharge during film formation
There is nothing to receive.   In addition, the method for forming a deposited film of the present invention uses silicon and halogen.
Of the deposited film obtained by decomposing the compound (SX) containing
Active Species (A) Containing Constituent Elements that Become Component Elements and Chemistry for Film Formation
Utilizing the reaction with active species (B) generated from substances,
Since the product does not need high temperature, the structure is not disturbed by heat.
No need for heating equipment and costs associated with its operation during production
Therefore, the cost of the device can be reduced. And resistant
A wide range of substrate materials that do not depend on thermal properties can be selected.   In addition, the method of forming a deposited film of the present invention uses the active species (A) and active species (A).
Of the substrate for forming the deposited film by the reaction with the sex species (B)
It is possible to increase the area regardless of shape and size, and at the same time,
Since the raw material is very small and the film formation space can be made small,
The rate can be dramatically improved.   In the deposited film forming method of the present invention, the nuclei for crystal growth are arbitrarily
The size of the crystal grain can be determined by arranging it on the substrate.
Deposit a crystalline deposited film with characteristics tailored to the desired area
Rukoto can.   Further, according to the deposited film forming method of the present invention having the above-described configuration,
At the same time as saving energy in forming deposited films
In addition, film quality is easy to control and uniform
It is possible to form a good crystalline deposited film with
You. In addition, it is excellent in productivity and mass productivity, high quality, electrical and optical.
Effective crystalline deposited film with excellent characteristics such as
Can be obtained efficiently. [Description of Embodiment Example]   In the present invention, the activation space (A) introduced into the film formation space
Is the active species (A) from the point of productivity and ease of handling?
, Its life is 0.1 seconds or more, more preferably 1 second or more,
Optimally, 10 seconds or more should be selected and used as desired.
Used to form the active species (A) component in the film formation space
The constituents of the deposited film are formed.
Also, the chemical substances for film formation are activated in the activation space (B).
Activated by being acted upon by energy and become active species (B)
Is introduced into the film formation space, and when the deposited film is formed, it is activated at the same time.
Structure of deposited film that is introduced and formed from activation space (A)
Chemically interacts with active species (A) containing constituent components
Works.   Containing silicon and halogen introduced into the activation space (A)
Examples of the compound include a chain or cyclic silane compound
In which some or all of the hydrogen atoms of are replaced with halogen atoms
A compound is used, and specifically, for example, Si_uY_{2u + 2}(U is
1 or more positive number, Y is a small number selected from F, Cl, Br and I
It is at least a kind of element. ) Chain halogenation
Silicon, Si_vY_2V(V is a positive number greater than or equal to 3 and Y has the above meaning.
Have. ) Cyclic silicon halide, Si_uH_xY_y
(U and Y have the above-mentioned meanings. X + y = 2u or 2u +
2. ) Chain or cyclic compounds represented by
Can be   Specifically, for example, SiF_Four, (SiF_Two)_Five, (SiF_Two)₆,
(SiF_Two)_Four, Si_TwoF₆, Si_ThreeF₈， SiHF_Three， SiH_TwoF_Two， SiCl_Four, (S
iCl_Two)_Five， SiBr_Four, (SiBr_Two)_Five, Si_TwoCl₆, Si_TwoBr₆, SiHC
l_Three， SiH_ThreeCl, SiH_TwoCl_Two， SiHBr_Three， SiHi_Three, Si_TwoCl_ThreeF_ThreeSuch as
Including those in a gas state or easily gasifiable
However, in the present invention, Si_TwoF₆Is used.   In order to generate the active species (A), the above silicon and ha
In addition to a compound containing a rogen, if necessary, silicon alone
And other silicon compounds, hydrogen, halogen compounds (eg F_Two
Gas, Cl_TwoGas, gasified Br_Two, I_TwoEtc.)
be able to.   In the present invention, the active species (A) is added in the activation space (A).
As a method of generation, consider each condition and device and
Electric energy such as microwave, RF, low frequency, DC, heater
No heat energy or light energy due to heat, infrared heating, etc.
Which activation energy is used.   Generate active species (B) in the activation space (B)
As the chemical substance for the film formation, hydrogen gas and / or ha
Rogengas (eg F_TwoGas, Cl_TwoGas, gasified Br_Two,
I_TwoEtc. are preferably used, but in the present invention, H_TwoUsed by
Can be In addition to these film-forming chemicals,
For example, using an inert gas such as helium, argon, or neon
Can be Uses multiple of these deposition chemicals
If it is present, mix it in advance with gas in the activation space (B).
Can be introduced in the state, or the film formation of these
Chemicals for use in gaseous form from individual sources
Alternatively, it can be introduced into the activation space (B), or
Introduce into each independent activation space and activate each individually
You can also do it.   In the present invention, the active species introduced into the film formation space
The ratio of the amounts of (A) and the active species (B) depends on the film forming conditions,
The type of active species, etc. can be appropriately determined according to the desire.
More preferably, 10: 1 to 1:10 (introduction flow rate ratio) is appropriate.
It is preferably 8: 2 to 4: 6.   In addition, the deposited film formed by the method of the present invention is
Alternatively, after the film formation, the impurity element in the so-called semiconductor field
It is possible to As an impurity element to use
Is an element of Group IIIA of the periodic table as a p-type impurity, eg
For example, B, Al, Ga, In, Tl and the like are mentioned as preferable ones, and n
As a type impurity, an element of Group V A of the periodic table such as P,
As, Sb, Bi and the like are mentioned as preferable ones, but especially B, G
a, P, Sb, etc. are optimal. Amount of impurities to be doped
Is determined according to the desired electrical and optical characteristics.
It is.   Substances containing such impurity elements as components (impurity introduction
As a substance to be used, it is in a gas state at normal temperature and pressure, so
Is a gas at least under activation conditions,
It is preferable to select a compound that can be easily vaporized by an ionization device.
New PH as such a compound_Three, P_TwoH_Four, PF_Three, PF_Five, P
Cl_Three, AsH_Three, AsF_Three, AsF_Five， AsCl_Three， SbH_Three, SbF_Five， SiH_Three, BF
_Three, BCl_Three， BBr_Three, B_TwoH₆, B_FourH_Ten, B_FiveH₉, B_FiveH₁₁, B₆H_Ten, B₆
H₁₂， AlCl_ThreeEtc. can be mentioned. Contains impurity elements
The compounds may be used alone or in combination of two or more.   Compounds containing impurity elements as components are
It does not matter if it is introduced into the deposition space, or in advance.
Activation space (A) or activation space (B), or the third
Activated in the activation space (C) and then introduced into the film formation space
It can also be grown at the time of polycrystal growth containing Si or Si.
There is a plane orientation dependence of velocity. This is the film deposition method or
Depending on the case, (110)> (111) in the method of the present invention
> (100) is clear by the present inventor
I was killed. Under these conditions, the deposition film formation conditions should be selected appropriately.
By doing so, stronger orientation, ie (110) >> (111)
≫ The condition of (100) can be realized. The present invention
In particular, a part for promoting nucleation is provided on the substrate.
As a result, the orientation is stronger and the growth rate is faster.
Is possible. Then, only the (110) plane is distributed.
It is possible to form a polycrystalline film with a large grain size.
Select the size, shape, spacing, material, etc. of the nucleus
By doing so, it is possible to grow a single crystal.   In the method of the present invention, a desired crystalline deposited film is selected.
Crystal nuclei are selectively formed beforehand
Materials that can be formed must be arranged on the surface of the substrate in a desired manner.
It is necessary.   Crystal morphology nuclei depending on the type of crystallization surface forming material
Utilize the difference in density to form a nucleus in a desired pattern on the substrate
Selectively desired by arranging the surfaces in discrete positions
It is possible to form a crystalline deposited film of   For example, select a silicon single crystal by covering it with a silicon oxide film.
Alternatively, an underlying silicon single crystal is exposed, or
SiO with small crystal growth_TwoThin silicon nitride on the substrate
A membrane in which a minute area is selectively arranged is used. Sa
In addition, as described above, instead of this silicon crystal, silicon
Different types of crystals can be used as nuclei, but these
The following conditions are required for the crystalline material. 1. The lattice constant of the crystalline material on the substrate surface is the same as the lattice constant of the deposited film.
Match or very close. 2. The coefficient of thermal expansion of the crystalline material on the substrate surface and the deposited film are the same
Or very close.   Therefore, a suitable substrate surface for obtaining a crystalline Si deposition film
GaF_Two, ZnS, Yb, Mn_ThreeGa, NaCo
F_Three, Ni_ThreeSn, Fe_ThreeC, NiTex (x <0.7), CoMnO_Three， NiMnO_Three,
MaZn_Three, CuCl, AlP, Si and the like.   Furthermore, even if the above two conditions are substantially deviated,
Crystalline deposition film by more appropriate selection of deposition conditions
It is also possible to use the above-described material
However, the present invention is not limited to this.   For example, the groups used to obtain Si crystals in the present invention
As the body, for example, SiO_TwoSi on film_ThreeN_FourDiscretely
Tata or Si_ThreeN_FourSiO on the film_TwoCover with, partly base S
i_ThreeN_FourIs used.   This is because the silicon crystal nucleus is Si_ThreeN_FourEasy to form on top, SiO_Two
The deposited film of the present invention, which utilizes the properties that are difficult to generate above
In the formation method, it is a material having difficulty in forming nucleation.
Can be used irrespective of whether it is amorphous or crystalline.
You.   Substrate temperature during film formation (T_S) Indicates the type of deposited film to be formed and
It is set as appropriate depending on the type of substrate used.   Next, in order to better understand the present invention, metal and semiconductor
A general thin film forming process will be described.   The type of material different from the atom from which the deposition surface is flying, especially amorphous
If the material is a porous material, the flying atoms freely spread over the substrate surface.
Disperse or re-evaporate (desorb). And the collision of atoms
, A nucleus is formed and its free energy G is maximized
Size rc (= -2σ) of such a nucleus (critical nucleus)₀/ gv)
Then, G decreases and the nucleus continues to grow stably three-dimensionally.
And it becomes an island. A nucleus larger than rc is called a "stable nucleus"
In the basic explanation of the present invention after the call, anything is refused
"Nucleus" without "and" means this "stable nucleus"
Shall be.   In addition, those with small r in “stable nuclei” are called “initial nuclei”.
Call. Free energy G caused by nucleation
Is G = 4πf (θ) (σ₀r^Two+1/3 ・ gv ・ r^Three) f (θ) = 1/4 (2-3 cos θ + cos^Twoθ) Where r is the radius of curvature of the nucleus         θ: Contact angle of nucleus         gv: Free energy per unit deposition         δ₀: Surface energy between nucleus and vacuum It is expressed as FIG. 1 shows how G changes. In the figure
Where the radius of curvature of the stable nucleus when G is the maximum value is rc
It is.   In this way, the nucleus grows into an island, and further grows into an island
Communicating with each other progresses, and in some cases coalescence occurs,
Finally, a continuous film is formed through the eye-like structure to completely cover the substrate surface.
cover. Through such a process, a thin film is deposited on the substrate.   In the deposition process as described above, the unit surface of the substrate surface
Density of nuclei formed per product, size of nuclei, nucleation rate
Is determined by the state of the system of deposition, especially the incoming atoms and the substrate surface.
Interaction with surface material is an important factor. Also sediment
Anisotropy of the interfacial energy of the interface between the material and the substrate with respect to the crystal plane
Depending on the position, a certain crystal orientation grows parallel to the substrate
However, if the substrate is amorphous,
The azimuth is not constant. For this reason, nuclear or island comrades
Grain boundaries are formed by collisions, especially over a certain size
In the event of a collision between two islands, when coalescence occurs, the grain boundaries remain
It is formed. The formed grain boundaries are difficult to move in the solid phase
For that, the particle size is determined at that point.   Next, selective deposition to selectively form a deposited film on the deposition surface
The law is described. The selective deposition method is the surface energy
Thin film formation process such as adhesion coefficient, desorption coefficient, surface diffusion rate, etc.
Using the difference between the materials of the factors that affect nucleation in
In this method, a thin film is selectively formed on a substrate.   2 (A) and 2 (B) are explanatory views of the selective deposition method.
You. First, as shown in FIG.
And a thin film 2 made of a material having the above-described factors different from each other in a desired portion.
To achieve. And, depending on the appropriate deposition conditions,
When a thin film composed of thin films is deposited, the thin film 3 is formed only on the thin film 2.
Cause a phenomenon that the substrate does not grow on the substrate 1
be able to. By utilizing this phenomenon,
Can grow the thin film 3 formed into
Lithography process using a resist such as
Become.   Materials that can be deposited by such a selective formation method
For example, as the substrate 1, SiO_TwoSi, GaA as the thin film 2
s, silicon nitride, and Si, W, G as the thin film 3 to be deposited
aAs, InP, etc.   FIG._TwoBetween the silicon deposition surface and the silicon nitride deposition surface
It is a graph which shows a time-dependent change of nucleation density (ND).   As the graph shows, shortly after the start of deposition, SiO_Two
Nucleation density (ND) above is 10^Threecm^-2Less than 20 minutes
Even after that the value hardly changes.   In contrast, silicon nitride (Si_ThreeN_Four) Above, about 4 × 1
0^Fivecm^-2At once, then does not change for about 10 minutes,
After that, it increases rapidly. In this measurement example, Si
Cl_FourH gas_TwoDiluted with gas, pressure 175 Torr, temperature 1000 ℃
The figure shows a case where deposition is performed by the CVD method under the conditions.   Such a phenomenon is caused by SiO_TwoSurface of silicon and silicon nitride
In adsorption coefficient, desorption coefficient, surface diffusion coefficient, etc.
Is large, but the Si atoms themselves_TwoBut anti
In response, silicon monoxide with a high vapor pressure is generated,
O_TwoIt is etched by itself, while on Silicon Nitride this
Selective deposition also means that no such etching phenomenon occurs.
(T.Yonehar
a, S.Yoshioka, S.Miyazawa Journal of Applied physics
 53,6839,1982).   Thus, SiO as the material of the deposition surface_TwoAnd Silco nitride
If you select silicon and silicon as the deposition material,
Large enough nucleation density difference (ΔND) as shown in the graph
Can be obtained. Here, the material of the deposition surface is
T SiO_TwoIs desirable, but not limited to this, SiOx (0 <x <2)
However, a sufficiently practical nucleation density difference (ΔND) can be obtained.
Can be.   Of course, it is not limited to these materials,
The difference in density (ΔND) is the nuclear density as shown in the same graph.
Ten^ThreeMore than double is sufficient, a material as exemplified later
Depending on the material, sufficient selective formation of deposited film can be performed.
You.   Another method for obtaining this nucleation density difference (ΔND) is Si
O_TwoSurface is locally ion-implanted with Si, N, etc.
You may form the area | region which has etc.   The present invention is based on such a nucleation density difference (ΔND),
Selective deposition is used, and the material on the deposition surface
Deposition surface made of dissimilar material with sufficiently high nucleation density
To form fine enough to grow only one nucleus
Therefore, a single bond is formed only at the place where the fine different material exists.
The crystal is selectively grown.   The selective growth of the single crystal depends on the electronic shape of the deposition surface.
State, especially the state of the dangling bond
For materials with low nucleation density (eg SiO 2_Two) Is Bar
The material does not have to be
It may be formed only to form the above-mentioned deposition surface.   Hereinafter, the present invention will be described in detail with reference to the drawings.   4 (A) to 4 (D) show how to form a crystal according to the present invention.
FIG. 5 is a formation process diagram showing a first embodiment example of the method, and FIG.
(A) and (B) are shown in FIGS. 4 (A) and (D).
FIG.   First, as shown in FIGS. 4 (A) and 5 (A),
A low nucleation density enabling selective nucleation on the substrate 4
Thin film 5 [Nucleated surface (S_NDS)] Forming a nucleus on it
A material different from the material forming the thin film 5 having a small formation density
Thinly deposited and patterned by lithography etc.
The nucleation surface (S_NDL) (Or "Se
6) is formed sufficiently fine. However, the size of the substrate 4
Any size, crystal structure and composition can be used
A substrate on which functional elements made by conductor technology are formed,
Is also good. In addition, the nucleation surface (S_NDL6)
Is formed by ion-implanting Si or N into the thin film 5 as described above.
Includes altered regions having excess Si, N, etc. formed
And   Next, by selecting appropriate deposition conditions by the FOCVD method,
To form a crystalline deposition film. That is, first, the nucleation surface
(S_NDLAnd (6) only a single core of thin film material is formed. Nuclear
Forming surface (S_NDL) The size of 6 depends on the type of material.
However, it may be a few microns or less. Furthermore, the nucleus is a single crystal structure.
It grows while maintaining its structure, and has an island shape as shown in FIG. 4 (B).
Becomes single crystal grains 7. Island-shaped single crystal grains 7 are formed.
As described above, the nucleation on the thin film 5 does not occur at all.
It is desirable to decide the conditions so that it does not happen
You.   The island-shaped single crystal grains 7 form nuclei while maintaining the single crystal structure.
Surface (S_NDL) 6 and grow further (later alovergr
owth), covering the entire thin film 5 as shown in FIG.
Can be done. (Single crystal 7A).   Then, if necessary, simply etching or polishing
The crystal 7A is flattened and shown in FIGS. 4 (D) and 5 (B).
Thus, the single crystal layer 8 capable of forming a desired element is
It is formed on the thin film 5.   In this way, the non-nucleating surface (S_NDSThe thin film 5 forming
Since it is formed on the plate 4, the substrate 4 that serves as a support is optional.
Any material can be used. In this case
Functional elements etc. are formed on the substrate 4 by ordinary semiconductor technology.
A single crystal layer 8 can be easily formed on it
You can do it.   In the above embodiment, the non-nucleation surface (S_NDS) A thin film
5, but of course, as shown in FIG.
Of low nucleation density (ND) material that enables
The nucleation surface (S_NDL) As desired
The single crystal layer may be formed at an arbitrary position and formed in a similar manner.   6 (A) to 6 (D) show a second embodiment of the present invention.
FIG. 4 is a process chart for forming the crystal shown. As shown in the figure, select
From materials with low nucleation density (ND) that enable nucleation
On the substrate 9 made of a material having a high nucleation density (ND).
Nucleation surface (S_NDL) 6 is made sufficiently small,
The single crystal layer 8 can be formed in the same manner as in one embodiment.
it can.   7 (A) to 7 (D) show how to form a crystal according to the present invention.
FIG. 8 is a forming process diagram showing a third embodiment example of the method, and FIG.
(A) and (B) correspond to FIGS. 7 (A) and (D).
FIG.   As shown in FIGS. 7 (A) and 8 (A),
Nuclei are formed on a porous insulator substrate 11 at a distance l.
The nucleation surface (S_NDL) 12
-1, 12-2 are arranged sufficiently small. This distance l is
For example, it is necessary to form a semiconductor device or a group of devices.
Set to be equal to or larger than the size of the single crystal region
It is.   Next, by selecting appropriate crystal formation conditions,
Nucleation surface (S_NDL) Nuclei of crystal forming material only in 12-1 and 12-2
Only one is formed. That is, the nucleation surfaces 12-1 and 12-2 are simply
The size (surface) is fine enough to form only one nucleus.
Product). Nucleation surface (S_NDL) 12-1,12
The size of -2 depends on the type of material,
Ron or less. Furthermore, the nucleus must not maintain a single crystal structure.
As shown in FIG. 7 (B), island-like single crystal grains
It becomes 13-1, 13-2. Island-shaped single crystal grains 13-1, 13-2
In order to be formed, as already mentioned, on the substrate 11
Nucleation surface (S_NDLNo nucleation occurs on surfaces other than
It is desirable to determine the conditions so that   The connection of the island-like single crystal grains 13-1 and 13-2 in the normal direction of the substrate 11
The crystal orientation is determined by the interface between the material of the substrate 11 and the material forming the nucleus.
It is fixed to minimize the energy. Because
Surface or interface energy is illegal depending on the crystal plane
This is because However, as already mentioned
In the amorphous substrate, the crystal orientation in the substrate plane is determined.
Absent.   The island-like single crystal grains 13-1 and 13-2 grow further and
Crystals 13A-1 and 13A-2 become adjacent, as shown in Fig. 7 (C).
Single crystals 13A-1 and 13A-2 contact each other, but
The nucleation surface (S_NDL) 12
A grain boundary 14 is formed at an intermediate position between -1 and 12-2.   Subsequently, the single crystals 13A-1 and 13A-2 grow three-dimensionally.
However, the crystal plane with a slow growth rate appears as a facet.
You. Therefore, single crystal 13A by etching or polishing
The surface of -1,13A-2 is flattened, and the grain boundary 14
Is removed, as shown in FIGS. 7 (D) and 8 (B).
A single-crystal thin film 15-1, 15-2, 15 without grain boundaries
Formed. The size of this single crystal thin film 15-1, 15-2, 15
Is the nucleation surface (S_NDL) By 12 intervals l
Is determined. That is, the nucleation surface (S_NDL) 12 forming pa
Control the position of grain boundaries by appropriately setting turns
A single crystal of a desired size in a desired arrangement.
Can be formed.   9 (A) to 9 (D) show a fourth embodiment of the present invention.
FIG. 4 is a process chart for forming the crystal shown. As shown in FIG.
Selective nucleation can be performed on the desired substrate 4 as in the embodiment.
Thin film made of material with low nucleation density (ND)
Non-nucleation surface (S_NDS) 5 is formed, and on it the nucleus in problem l
Nucleation surface (S
_NDL) 12 is formed, and a single film is formed in the same manner as in the third embodiment.
Crystals 15 can be formed.   10 (A) to 10 (C) show how to form a crystal according to the present invention.
FIG. 11 is a forming process diagram showing a fifth embodiment example of the method, and FIG.
(A) and (B) correspond to FIGS. 10 (A) and (C).
It is a perspective view of a substrate.   First, as shown in FIGS. 10 (A) and 11 (A),
The amorphous insulator substrate 11 has a recess 16 of a desired size and shape.
Are sufficiently small that only a single nucleus can be formed therein.
Small size nucleation surface (S_NDL) Forming 12.   Subsequently, as shown in FIG. 10 (B), the first embodiment example
In the same manner as described above, island-like single crystal grains 13 are grown.   Then, as shown in FIG. 10 (C) and FIG. 11 (B).
Then, the single crystal grains 13 are grown until they fill the concave portions 16, and the single crystal
The layer 17 is formed.   In this embodiment, the single crystal grains 13 grow in the concave portions 16.
In addition, the steps of flattening and removing the grain boundary portion are not required.   FIGS. 12A to 12C show a sixth embodiment of the present invention.
FIG. 4 is a process chart for forming the crystal shown. As shown in FIG.
It is possible to form selective nuclei on any substrate 4 similar to the embodiment.
Thin film made of material with low nucleation density (ND)
Non-nucleation surface (S_NDSA) form the desired size there
And a concave portion 16 having the same shape. And in it is non-nuclear
Forming surface (S_NDS) Is a heterogeneous material.
Nucleation surface made of material with high nucleation density (ND)
(S_NDL) 12 is formed minutely and is similar to the fifth embodiment.
To form a single crystal layer 17.   13 (A) to 13 (C) show a seventh embodiment of the present invention.
FIG. 4 is a process chart for forming the crystal shown. Form a recess in the desired substrate 19
Nucleation density sufficient to allow selective nucleation
Non-nucleated surface in the form of a thin film made of a material with a small (ND)
(S_NDS20) to form a single crystal in the same manner as in the above example.
Layer 17 can be formed.   FIG. 14 is manufactured using the first embodiment example of the present invention.
Schematic diagram showing an example of a semiconductor electronic device having a multilayered structure
FIG.   In the figure, a semiconductor substrate 1401 of Si or GaAs has
Transistor 1402 and other
A semiconductor element or an optical element is formed, and a CVD method or
By the sputter method, for example, the non-nucleation surface (S_NDS) 1404
Having SiO_TwoA layer 1403 is formed. And already mentioned
As described above, the area is small enough that only a single nucleus can be formed.
Nucleation surface (S_NDLExample) Thin film 1406 with 1405
Ba Si_ThreeN_FourAnd the nucleation surface (S_NDL) Single crystal from 1405
Is grown to form a Si single crystal layer 1407.   Subsequently, the transistor 1408 and the other half are added to the single crystal layer 1407.
Form conductor element or optical element, SiO_TwoSubstrate through layer 1403
The elements formed on 1401 and Si single crystal layer 1047, respectively, are electrically
Connect to Thus, for example, the first layer (substrate 1401)
Transistor of transistor 1402 and second layer (single crystal layer 1404)
Each of the transistors 1408 and 1408 is formed as a MOS transistor.
If you connect them to form CMOS, CM without any interaction
OS can be manufactured. In addition, the same technology as above
Therefore, the light emitting element and its driving circuit are integrally formed.
It is also possible to achieve high integration.   Further, by repeating this embodiment, SiO 2_TwoAcross layer 1403
The single crystal layer 1407 can be formed in any number of layers, and can be easily and
A layered semiconductor electronic device can be formed.   FIGS. 15A to 15D show an eighth embodiment of the present invention.
FIG. 4 is a process chart for forming the crystal shown.   FIGS. 7A to 7C are the same as FIGS. 7A to 7C.
It is. That is, a plurality of nucleation surfaces 12
(2 in the figure) and overgrowth on the nucleation surface 12
A single crystal grain 13 is formed. This single crystal grain 13 is further grown.
Nucleation surface by forming single crystal 13A
(S_NDL) A grain boundary 14 is formed almost at the center of 12, and a single crystal 13A
By flattening the surface of the particles, the particles as shown in FIG.
A polycrystalline layer 21 having a diameter substantially equal to 1 can be obtained.   The grain size of this polycrystalline layer 21 is determined by the nucleation surface (S_NDL) 12 intervals l
Control of the polycrystalline particle size
Become. Conventionally, the grain size of the polycrystal is determined by the forming method, forming temperature, etc.
Polycrystals that vary with multiple factors and have a large grain size
When creating a particle, it has a particle size distribution with a width
According to the present invention, the distance l between the nucleation surfaces 12 is
The particle size and the particle size distribution are determined with good controllability.   Of course, as shown in FIG.
Non-nucleation surface with small degree (ND) (S_NDS) 5 and nucleation density
(ND) Large nucleation surface (S_NDL) Forming 12-1,12-2
Thus, the polycrystalline layer 21 may be formed. In this case,
As described in the above, there is no restriction on the substrate material, structure, etc.
Therefore, the polycrystalline layer 21 can be formed with a limited grain size and grain size distribution.
Can be.   Next, the single crystal layer or the multiple bonding in each of the above embodiments is described.
The specific method of forming the crystal layer is shown in FIG.
More specifically, the example of the eighth embodiment shown in FIG.
This will be described in more detail.   Thermal oxidation of a Si single crystal wafer to form SiO on the surface_TwoForm a layer
The surface is non-nucleated (S_NDS) Substrate 11.
Of course, a quartz substrate, which is a material with a low nucleation density (ND),
It may be used as the substrate 11, or may be a metal, a semiconductor, a magnetic material,
A spatter is placed on the surface of any underlying substrate such as a piezoelectric or insulator.
SiO using the CVD method, CVD method, vacuum evaporation method, etc._TwoNucleation by forming layers
Surface (S_NDS) May be provided. Also, non-nucleated surface
(S_NDS) Is formed of SiO_TwoIs preferable, but Si
The value of X is changed as Ox (0 <x <1).
You may.   SiO thus formed_TwoSi of the substrate 11 having a layer on the surface
O_TwoA silicon nitride layer (eg,
Ba Si_ThreeN_Four) Layer or polycrystalline silicon layer, and then
Conventional lithographic techniques or X-ray, electron beam or ion
Silicon nitride layer or multi-layer
Pattern the crystalline silicon layer, preferably 10μ or less
Below, more preferably less than a few microns, optimally less than 1 μm
Nucleation surface (S_NDLTo form 12)
You.   Subsequently, for example, an appropriate gas is selected from the gas types described above.
The FOCVD method is used to select, for example, S on the substrate 11.
Selectively grow i single crystal. Substrate temperature and pressure at that time
The force etc. is appropriately determined as desired, but as the substrate temperature
Is preferably 100 to 600 ° C.   After several tens of minutes, the SiO_TwoA silicon nitride layer on the layer or
Nucleation surface consisting of polycrystalline silicon layer (S_NDSMainly on 12)
And select the optimal growth conditions to obtain single crystal Si grains 13
Grow to a size of several tens μm or more.   Then Si and SiO_TwoUtilizing the difference in etching speed between
By reactive ion etching (RIE), only Si
Selective etching to flatten the surface of single crystal 13A
As a result, a polycrystalline silicon layer 21 having a controlled grain size is formed.
(FIG. 15D). Further removing the grain boundary part
A single-crystal silicon layer 15 is formed (FIG. 7 (D)). What
If the surface of the single crystal grain 13 has large irregularities,
Etching may be performed after polishing.   Grain boundaries with a size of several tens μm or more formed in this way
Normal semiconductor device fabrication on the single crystal silicon layer 15
When field effect transistors are formed using
Shows characteristics comparable to those formed on crystalline silicon wafers
You.   The adjacent single crystal silicon layers 15 are made of SiO._TwoElectricity of etc.
If they are electrically separated by a static insulator, the complementary electric field
Even if the effect transistor (C-MOS) is configured,
It is possible to prevent communication. Also, the activity of the element to be formed
Since the layer thickness is thinner than with Si wafers,
There is no malfunction due to electric charges generated when the rays are irradiated.
Become. Furthermore, because the parasitic capacitance is reduced, the device speed is increased.
Can be achieved. Also, since any substrate can be used, Si wafer
A single crystal layer with a low cost can be used on a large-sized substrate, rather than using
Can be formed of In addition, other semiconductors, piezoelectric
To form a single-crystal layer on a substrate such as a body or dielectric
Furthermore, a multifunctional three-dimensional integrated circuit can be realized.   Thus, the present invention exhibits a number of excellent effects. (Composition of silicon nitride)   The non-nucleation surface (S_NDS) Forming material
(M_S) And nucleation surface (S_NDL) Forming material (M_L) And enough nuclear
To obtain the formation density difference (ΔND), use polycrystalline silicon or SiO._Two
Nucleation surface (S_NDS) Forming material is Si_ThreeN_FourLimited to
The chemical composition of silicon nitride is not specified.
You may use what changed the ratio.   To change the chemical composition ratio of silicon nitride, for example,
Do as follows.   SiH in RF plasma_FourGas and NH_ThreeDecomposed with gas and low temperature
The plasma CVD method of forming a silicon nitride film with_Four
Gas and NH_ThreeBy changing the flow ratio with the gas,
The composition ratio of Si and N in the silicon nitride film
be able to.   Figure 16 shows the SiH_FourAnd NH_ThreeFlow rate ratio and formed silicon nitride
An example of the relationship between the composition ratio of Si and N in the copper film was shown.
It is a graph.   The deposition conditions at this time were as follows: RF output 175 W, substrate temperature 380 ° C
Yes, SiH_FourThe gas flow rate is fixed at 300 cc / min and NH_ThreeGas flow
The amount was varied. As shown in the graph, NH_Three/ SiH_FourMoth
When changing the flow rate ratio from 4 to 10
The Si / N ratio varies from 1.1 to 1.58 by Auger electron spectroscopy.
Revealed by law.   In addition, SiH_TwoCl_TwoGas and NH_ThreeIntroduce gas
Formed at a temperature of about 800 ° C under a reduced pressure of 0.3 Torr.
The composition of the silicon nitride film is almost stoichiometric._ThreeN_Four(S
i / N = 0.75).   Also, Si is converted to ammonia or N_TwoHeat treatment at about 1200 ℃
Nitride film formed by processing (thermal nitridation method)
Is further developed because the formation method is performed under thermal equilibrium.
A composition close to the stoichiometric ratio can be obtained.   As described above, silicon nitride formed by various methods
Nucleation density is SiO_TwoHigher nucleation surface (S_NDL) With forming material
Nucleation of silicon nitride
Surface (S_NDL) When grown on, the chemical composition of silicon nitride
Based on the difference in nucleation density (ΔND) depending on the ratio, the Si single crystal
It is formed.   Figure 17 shows the relationship between the Si / N composition ratio and the nucleation density (ND).
This is a graph. As shown in the graph, silicon nitride
By changing the chemical composition ratio of the film, it is formed on it.
The nucleation density of the Si single crystal nuclei is drastically changed. Fig. 17
The nucleation conditions in the graph are SiCl_FourGas reduced to 175 Torr
Press and hold at 1000 ℃ for H_TwoReacts with to generate Si single crystal nuclei
Is the case. Of course, nucleation conditions such as gas species, pressure, temperature
It goes without saying that different graphs can be obtained by changing the degree, etc.
not.   Thus, the nucleation density depends on the chemical composition ratio of silicon nitride.
The change in degree is sufficient to grow a single nucleus.
Finely formed nucleation surface (S_NDL)
When silicon nitride is used, the nucleation surface (S_NDL)of
Affects size (area). That is, the nucleation density
When using silicon nitride with a composition with a large (ND)
Has a nucleation surface (S_NDL) Is the nucleation density (ND)
Much finer than relatively small silicon nitride
Nucleation surface (S_NDLSingle on
Only nuclei can be formed.   Such a point is the nucleation surface (S_NDL) To other materials forming
However, the same tendency can be applied.   Therefore, in the present invention, the purpose is effectively achieved.
Nucleation density (ND) to form a single nucleus
Nucleation surface (S_NDL)of
It is desirable to appropriately select the size and the size as desired.
For example ~ 10^Fivecm^-2Nucleation line to obtain the nucleation density (ND) of
In some cases, the nucleation surface (S_NDL) Size
If it is about 4 μm or less, only a single nucleus is selectively formed.
can do.   In that case, the Si / N composition ratio is about 0.5. (Nucleation surface by ion implantation (S_NDL) Formation)   Nucleation density difference (ΔND) when forming Si single crystal nuclei
Another way to do this is to use non-nucleation with low nucleation density.
Surface (S_NDSSiO)_TwoLocal to the surface of the layer
Into Si, N, P, B, F, Ar, He, C, As, Ga, Ge, etc.
_TwoAn altered area of a desired size is formed on the layer surface,
Nucleation area (S) with large nucleation density (ND)_NDL)
You can also.   For example, SiO_TwoCover the layer surface with a photoresist layer and
Exposure, phenomenon, dissolution of_TwoPartial layer surface
Express.   Then, SiF_FourUsing gas as source gas, Si ion
Is 1 × 10 at 10 keV¹⁶~ 1 × 10¹⁸cm^-2Exposed at a density of
SiO_TwoDrive into the layer surface.   In this case, the projection range is 114 ° and SiO_TwoLayer exposed surface
Then the Si concentration is ~ 10^{twenty two}cm^-3Reach SiO_TwoLayers are originally non
Since it is crystalline, Si ions were implanted to make it excessive.
The quality region is also amorphous.   In addition, in order to form the altered region, a resist is used as a mask.
Although ion implantation can be performed by
Squeezed without using a resist mask
Si ion beam to SiO_TwoWithin desired area at desired position on layer surface
May be selectively injected.   After performing the Si ion implantation in this manner, the remaining resist is removed.
By peeling, SiO_TwoAltered regions with excessive Si on the layer surface
It is formed at a desired position in a desired size. Such alteration
SiO with region formed_TwoSi single crystal on the altered area on the layer surface
Is vapor-phase grown.   Fig. 18 shows the relationship between the implantation amount of Si ions and the nucleation density (ND).
It is a graph which shows a relationship.   As shown in the graph, Si⁺The higher the injection volume, the more nucleation
It can be seen that the density (ND) increases.   Therefore, it is necessary to form this altered region sufficiently fine.
In this alteration region, the nucleation surface (S_NDLA) single as
Only nuclei can be grown, and single crystals
Can grow.   Note that the altered region is sufficient to allow only a single nucleus to grow.
Fine patterning requires patterning of resist and collecting
Achieved easily by focusing the beam of the bundled ion beam
Is done.   19 (A) to 19 (D) show how to form a crystal according to the present invention.
FIG. 20 is a forming process chart showing a ninth embodiment example of the method, and FIG.
(A) and (B) correspond to FIG. 19 (A) and (D).
It is a corresponding perspective view.   First, as shown in FIG. 19 (A) and FIG. 20 (A)
Next, a nucleation density enabling selective nucleation is formed on the underlying substrate 4.
Thin film 6 (or called “Seed”) with a high degree [Nucleation surface
(S_NDL) Forming 6A], and nucleation density on it
A material different from the material forming the thin film 6 having a large thickness
And patterning by lithography
Made of dissimilar materials and non-nucleated surface (S_NDS) Thin to form 5A
The film 5 is placed on the nucleation surface (S_NDL) Make sure that 6A is fine enough
Formed. However, the size, crystal structure,
And composition may be arbitrary, and may be formed by ordinary semiconductor technology.
The substrate on which the created functional element is formed may be used. Ma
Nucleation surface (S_NDL6) SiO_TwoThin film 5
The thin film 6 underneath is made of polycrystalline silicon or SiO_TwoFormed and exposed
Excess Si formed by ion implantation of Si, N, etc. into part 6A
Alternatively, it may be formed as an altered region having N or N.   Next, nucleation by selecting appropriate deposition conditions
Surface (S_NDL) A single nucleus of crystal forming material is formed only in 6A
You. That is, the nucleation surface (S_NDL6A has only a single nucleus
It must be formed fine enough to be formed. Karyotype
Surface (S_NDL6) The size of 6A depends on the type of material
May be several microns or less. The nucleus has a single crystal structure
And grow in an island shape as shown in FIG. 19 (B).
Single crystal grains 7 are obtained. Because island-like single crystal grains 7 are formed
As described above, nucleation does not occur at all on the thin film 5A.
It is desirable to determine the conditions so that they do not
You.   The island-shaped single crystal grains 7 have a nucleation surface while maintaining a single crystal structure.
(S_NDL) Growing further around 6A (lateral over gro
wth), the entire surface of the thin film 5 is covered as shown in FIG.
Can be obtained (single crystal 7A).   Then, if necessary, simply etching or polishing
The crystal 7A was flattened, as shown in FIGS. 19 (D) and 20 (B).
As shown, a single crystal that can form the desired element
Layer 8 is formed on thin film 5.   Thus, the nucleation surface (S_NDL) The thin film 6 forming 6A is based
Since it is formed on the plate 4, the substrate 4 serving as a support is
Any material can be used. In such cases
Function elements etc. are formed on the substrate 4 by ordinary semiconductor technology.
Even if it is formed, the single crystal layer 8 is easily formed thereon.
Can be formed.   In the above embodiment, the nucleation surface (S_NDL) 6A thin
It was formed of the film 6, but of course, as shown in FIG.
Consisting of high nucleation density (ND) material
Using the substrate as it is, the non-nucleation surface (S_NDS)
And the single crystal layer may be formed in the same manner.
No.   The twenty-first (A) to (D) show the tenth embodiment of the present invention.
It is a formation process drawing of a crystal. As shown in the figure, the selected nucleus
Made of a material with a high nucleation density (ND)
The substrate 9 is made of a material with a low nucleation density (ND).
The non-nucleation surface (S_NDS) Nucleation of thin film 5 forming 5A
Surface (S_NDL) Provide a sufficiently small exposed portion of the substrate 9 to be 9A
A substrate for crystal formation is prepared by forming
The single crystal layer 8 is formed in the same manner as in the first embodiment using the
Can be achieved.   22 (A) to 22 (D) show how to form a crystal according to the present invention.
FIG. 23 is a formation process diagram showing an example of the eleventh embodiment of the method, and FIG.
(A) and (B) are oblique views corresponding to FIGS. 22 and (D).
FIG.   As shown in FIGS. 22 (A) and 23 (A),
Nucleation density (ND) on a suitable underlying substrate 10 such as
Relatively large Si_ThreeN_FourAmorphous insulator thin film 12 such as
Allows selective nucleation on the membrane 12 at a distance l
Heterogeneous with a small nucleation density for the material forming the thin film 12
Of the single nucleus by selectively forming the thin film 11 at the desired position with the material
Nucleation surface (S_NDL)
Place 12A-1 and 12A-2. This distance l is, for example, half
Single connection required to form a conductor element or group of elements
The size is set to be equal to or larger than the size of the crystal region.   Next, by selecting appropriate crystal formation conditions,
Nucleation surface (S_NDL) Only 12A-1 and 12A-2 are
Only one of the nuclei is formed. That is, as described above, the nucleation surface 12
A-1 and 12A-2 are fine enough to form only a single nucleus.
It must be formed in a small size (area). Nucleation surface
(S_NDL) The size of 12A-1 and 12A-2 depends on the type of material.
, But may be several microns or less. Further,
The formed nucleus grows while maintaining the single crystal structure, and Fig. 22
As shown in (B), island-shaped single crystal grains 13-1 and 13-2 are formed.
You. Due to the formation of island-shaped single crystal grains 13-1 and 13-2
Is the nucleation surface (S_NDL) 12A-1,12A-
Surfaces other than 2 [Nucleated surface ((S_NDS) 11A]
Hope to determine conditions so that nucleation does not occur at all
It is good.   In the normal direction of the thin film 12 of the island-like single crystal grains 13-1 and 13-2,
The crystal orientation is determined by the interface between the material of the thin film 12 and the material forming the nucleus.
It is fixed to minimize energy. Because
If the surface or interfacial energy is illegal depending on the crystal plane
This is because it has a property. However, I already mentioned
As described above, the crystal orientation in the amorphous surface is determined.
Absent.   The island-like single crystal grains 13-1 and 13-2 grow further and
Crystals 13A-1 and 13A-2 are next to each other as shown in Fig. 22 (C).
Single crystals 13A-1 and 13A-2 contact each other, but
Because the crystal orientation of each single crystal differs,
(S_NDL) A grain boundary 14 is formed at an intermediate position between 12-1 and 12-2.
It is.   Subsequently, the single crystals 13A-1 and 13A-2 grow three-dimensionally.
However, the crystal plane with a slow growth rate appears as a facet.
You. Therefore, single crystal 13
The surface of A-1, 13A-2 is flattened, and the part of grain boundary 14 is further
Is removed, as shown in FIGS. 22 (D) and 23 (B).
Single crystal thin films 15-1, 15-2, ...
Formed. The size of this single-crystal thin film 15-1, 15-2, ...
Is the nucleation surface (S_NDL) 12A-1, 12A-2
It is determined by the interval l. That is, the nucleation surface
(S_NDL) Determine the formation pattern of 12A-1 and 12A-2 appropriately
This makes it possible to control the position of the grain boundary,
Single crystals of the desired size can be formed
You.   FIGS. 24 (A) to 24 (C) show how to form a crystal according to the present invention.
FIG. 25 is a formation process diagram showing a twelfth embodiment example of the method, and FIG.
(A) and (B) correspond to FIGS. 24 (A) and (C).
It is a corresponding perspective view.   First, as shown in FIG. 24 (A) and FIG. 25, FIG.
A thin film is formed on the base substrate 10 in the same manner as shown in step (A).
12 and thin film 11 are provided, and the nucleation surface (S_NDL) 12A-1,12A-
2 and non-nucleating surface (S_NDS) Form 11A. Then the nucleus
Forming surface (S_NDL) At the position corresponding to 12A-1, 12A-2
So that recesses 14-1 and 14-2 of size and shape are provided
In addition, a material similar to the thin film 11 or a small material equivalent to or less than the material.
The thin film 11-1 is formed of a material having a high nucleation density. This
In this way, only a single nucleus is formed in the recesses 14-1 and 14-2.
Nucleation surface (S_NDL) 12A-1,12A
A substrate for crystal formation having -2 is formed.   Subsequently, as shown in FIG. 24 (B), the first embodiment example
In the same manner as above, island-like single crystal grains 13-1 and 13-2 were grown.
You.   Then, as shown in FIG. 24 (C) and FIG. 25 (B)
And the single crystal grains 13-1 and 13-2 are filled in the recesses 14-1 and 14-2.
To form single-crystal layers 15-1 and 15-2.   In the present embodiment, the single crystal grains 13-1, 13-1
Planarization and removal of grain boundaries due to growth of 13-2
The process can be eliminated.   FIGS. 26 (A) to (D) show a thirteenth embodiment of the present invention.
FIG. 4 is a process chart for forming the crystal shown.   (A)-(C) are the same as (A)-(C) in FIG.
The same. That is, the nucleation surfaces 12A-1 and 12A-2 are placed at the interval l.
Nucleation surfaces 12A-1 and 12A
-2 overgrown single crystal
The grains 13A-1 and 13A-2 are formed. The single crystal grains 13-1, 13-
2 is further grown to form single crystals 13A-1 and 13A-2.
And the non-nucleation surface (S_NDS) Grain boundary 14 near the center of 11A
Are formed, and the surfaces of the single crystals 13A-1 and 13A-2 are flattened.
As a result, as shown in FIG.
A polycrystalline layer 16 can be obtained.   The grain size of the polycrystalline layer 16 depends on the nucleation surface (S_NDL) 12A-1,12A
The grain size of the polycrystal, as determined by the spacing l of -2
Control becomes possible. Conventionally, the polycrystalline particle size
And changes due to multiple factors such as temperature and formation temperature
When creating polycrystals with a grain size, the
Nucleation according to the present invention
Surface (S_NDL) Good controllability due to l in the interval of 12A-1, 12A-2
The particle size and particle size distribution are determined.   Of course, as shown in FIG.
Non-nucleation surface (S) with low nucleation density (ND)_NDS) 5A
And the nucleation surface (S_NDL) 9A
Form a plurality at desired positions at desired intervals, and polycrystalline as above
A layer may be formed. In this case, as already mentioned,
Considering the difference in nucleation density (ΔND), the substrate material and structure
The polycrystalline layer and the particle size distribution
It can be formed by controlling.   Next, a typical example of a film forming apparatus embodying the method of the present invention
Will be explained.   FIG. 27 shows an example of a deposited film forming apparatus for carrying out the method of the present invention.
It is a fragmentary sectional view showing a schematic structure of an example.   In FIG. 27, 101 is a silicon thin film deposited inside.
Is a deposition chamber in which the exhaust port 106 is installed in the deposition chamber 101.
Connected to an exhaust system (not shown) through the desired deposition chamber 101
Can hold the pressure of. Excited species in the deposition chamber 101
(A) Radical introduction tube 102 containing Si and halogen
And the introduction tube 103 for the hydrogen radical that is the excited species (B) is
They are provided in pairs. Guide each radical
The inlet pipe is thick at the working chambers 108 and 108A, and the outlets 109 and 109A.
It has become thin. By the roller 110 in the deposition chamber 1
Substrate support 104 so as to be able to reciprocate in the direction perpendicular to the paper surface
Is held. And on the support 104,
The base 105 is held. Each power outlet from exit 109, 109A
Zical is mixed and reacted in the vicinity of the substrate in the deposition chamber 101 to react with the substrate.
Form a film on top. Radica containing silicon and halogen
And hydrogen radicals are heating furnaces not shown respectively.
Or radical generators such as plasma chambers
After being generated from the raw material gas, each of the inlet pipes 10
It is introduced into the working chambers 108 and 108A from 2,103. The amount is
Mass flow control on the gas source side from the furnace or plasma chamber
Controlled by the trawler.   The roller 110 moves the substrate 105 and rolls it over the entire surface of the substrate.
It is provided only by depositing a thin film of Kon.   The introduction pipe 111 has a chemical or physical etching activity.
It is an introduction pipe for another gas that has
Excited in the illustrated heating furnace / plasma furnace, the gas exits 11
Lead up to 4. Etching activity that attacks the membrane from outlet 114
The gas having the property is released, and the property of the film is not in the growth direction.
Selectively cleaves and eliminates bonds. Etching of active gas
In addition to using such a separate introduction pipe, the reaction with the raw material gas
In the case of low resistance, mix with raw material gas and introduce pipes 102, 103
It can also be introduced from.   Hereinafter, the present invention will be described in more detail with reference to Examples.
I do. Example 1   Using the film forming apparatus shown in FIG.
A deposited film was prepared by the method.   The base 118 was formed by the process shown in FIG.   First, a polycrystalline silicon substrate as shown in FIG.
201 is washed and then sputtered (in this case spa
Various thin film deposition methods other than the sputtering method, such as vacuum deposition
Method, plasma discharge method, MBE method, CVD method, etc.)
Therefore, deposit a silicon oxide thin film 202 on the entire surface of the substrate 201.
[Figure (B)].   Subsequently, the electron beam resist layer 203 is applied on the thin film 202.
[(C) in the figure], using a photomask with a desired pattern,
The sub-beam resist layer 203 is exposed to light, and the electron beam laser
The dist layer 203 was partially removed [(D) of the same figure].   The remaining electron beam resist layer 203A is used as a mask to remove acid.
Etching the silicon oxide thin film 202 to form a desired pattern.
A thin film 202A was formed [FIG. (E)].   Through the above steps, the crystal plane of the polycrystalline silicon
Has portions 201A exposed from the silicon oxide film at regular intervals
A substrate 118 was obtained. Silicon crystal exposed on the surface of substrate 118
The region of 201A was 3 μm in diameter and 15 μm apart.   Further, using this substrate 118, the device shown in FIG.
Deposition of crystalline silicon was carried out. silicon
And Si as source gas for radical formation containing halogen_TwoF
₆Flow rate of 100 SCCM in the reaction section kept at 800 ℃.
And then decomposed, then released from the introduction pipe 102 to the action chamber 108
did. Simultaneously with this, argon gas was introduced into the inlet pipe 111 to 150
Inject SCCM with 2.45 GHz microwave at 1.0 W / cm_TwoPower of
Introduced to cause a discharge, H_TwoDisassemble the
Released at a flow rate of 5 SCCM. The substrate temperature is 330 ° C and the pressure is 0.2 Tor.
A deposited film of about 2μ was obtained by keeping r.   Of the cross section of the crystalline silicon deposited film 205 obtained on the substrate 118.
A schematic diagram is shown in FIG. 28 (F).   The crystal grain boundary 205 is a crystal base without the silicon oxide layer.
The crystal grain support should be equidistant from the exposed part 201A of the plate 201.
Iz had been decided.   Further, using each of the obtained samples, an X-ray diffraction method and electron
When the crystallinity of the deposited film was evaluated by the line diffraction method,
It was confirmed to be a polycrystalline silicon film. Further
The grain size of polycrystalline silicon obtained by the Scherrar method is
It was about 25 ± 2 μm. Variation in crystal grain size is on the entire substrate
There was almost no.   Also, observe the surface condition of the sample with a scanning electron microscope.
As a result, the smoothness was good, there was no wavy pattern, etc.
It was ± 4% or less. Also, the crystalline Si deposition of the prepared sample
The mobility and conductivity of the film were measured by the Van der pauw method.
Each, 300 (cm / V ・ sec), 9 × 10^-6(S ・ cm^-1)so
there were. Example 2   The base 118 was formed by the process shown in FIG.   First, a uniform material as shown in FIG.
The glass substrate 201 is cleaned, and then the substrate is cleaned by the thermal CVD method.
Amorphous SiN (A-SiN) thin film 202 on the entire surface of plate 201
A film having a thickness of μm was formed [FIG.   Subsequently, laser annealing is performed on the A-SiN thin film 202.
N depending on device_TwoIn the atmosphere, the surface area of the A-SiN thin film 202 is
The surface layer of the A-SiN thin film 202 (about 1 μm deep)
To crystalline Si_ThreeN_Four(C-Si_ThreeN_Four) 203 was formed. [same
Fig. (C)].   At this time, the laser is Ar-cw laser 4880Å, Sukiyan speed
Irradiation was performed at a rate of 2.5 cm / sec and energy of 10 w. Then, this
C-Si_ThreeN_FourO on the surface of layer 203_TwoThe above laser ani in the atmosphere
Scanning device and selectively SiO 2_TwoForming layer 204
[Diagram (D)].   By the above steps, C-Si_ThreeN_FourLayers exposed at regular intervals
Part 203A and the other part is SiO_TwoBase covered with layer 204
Body 118 was formed. C-Si exposed on the surface of the substrate 118_ThreeN
_FourThe areas of layer 203A were 4 μm in diameter and 3 μm apart.   Further, using this substrate 118, the
Deposition of crystalline silicon was performed by the equipment shown in the figure.
Was.   The deposition conditions were the same as those in Example 1 except that the pressure was 0.1 Torr:
Under the same conditions as in Example 1 except that the substrate temperature was changed to 270 degrees.
Deposition was carried out.   The crystalline silicon deposited film 205 obtained on this substrate 118 is cut off.
A schematic view of the plane is shown in FIG. 29 (F).   The grain boundary 206 is SiO_TwoExposing the crystalline substrate 201, except for the layer 204
The grain size is determined so that it is equidistant from the part 203A.
Had been.   Further, using each of the obtained samples, an X-ray diffraction method and an electric
The crystallinity of the deposited film was evaluated by the sagittal diffraction method.
It was confirmed that it was a polycrystalline silicon film.
Grain size of polycrystalline silicon obtained by the Scherrar method
Was about 20 ± 0.5 μm.
There was almost no overall.   Also, observe the surface condition of the sample with a scanning electron microscope.
As a result, the smoothness was good, there was no wavy pattern, etc.
It was ± 4% or less. Also, the polycrystalline Si deposition of the obtained sample
The mobility of the film was measured by the Van der Pauw method, and it was 150 (c
m / V ・ sec), 5 × 10^-6(S ・ cm^-1)Met. Example 3   The same conditions as those of the sample Nos. 1 and 2 of Example 1 and Example 2
Depending on the situation, thin film transistors such as those shown in Fig. 31 (hereinafter TF
(Abbreviated as T) was created. The pattern of SiNH under the above conditions
0.5μ on polished glass (Corning # 7059) substrate 3001
A Si semiconductor polycrystalline layer 3002 having a thickness of m is deposited as shown in FIG.
After using the process of making the upper gate coplanar TET
FT created.   First, by the glow discharge method, P-doped
N to form the microcontact layer 3103⁺Layer (specific resistance δ1
1000 Å was deposited. Then Fotolin Graph
The active layer 3102 is left by the a.
Was etched to form the contact layer 3103. So
After the NH using glow discharge method_ThreeAnd SiH_FourDisassemble the base
Film thickness 3000Å, dielectric constant 67, electrical breakdown voltage 3 × 10 at 200 ℃⁶
V / cmV_FBA Si-N-H film to be an OV insulating layer was deposited.
After that, contact all 3105 for source and drain is opened.
And depositing 5000 Å by vacuum evaporation of Al as the upper electrode
Then, the source electrode 3107,
The gate electrode 3109 and the drain electrode 3108 were molded. Gate width
W and gate length L were 650 μ and 22 μ, respectively. Dray
Voltage to the source and gate electrodes
The characteristics when added while measuring were measured. Drain current I_D
− Drain voltage V_DIn terms of characteristics, both No. 1 and 2 have good saturation
The characteristics are obtained, and the gate voltage is 10V and the drain voltage is 10V.
7 × 10^-FourA high current of A is obtained. Gate voltage V_DTo
Vary drain current I_DObtained from the result of measuring
The TFT characteristics are shown in Table 1.   The TFT using the film obtained above has good characteristics.
It has been found. 〔The invention's effect〕   The method for forming a deposited film according to the present invention includes the active species (A) and the active species.
It is possible to form a deposited film only by bringing it into contact with (B).
And does not require external reaction excitation energy.
Therefore, the substrate temperature can be lowered.
It is also possible to achieve. Pre-deposit
The material that becomes the crystal nucleus of the film or the crystal nucleus can be selectively formed.
The desired material can be placed at the desired position on the substrate surface,
A crystalline deposited film can be formed. Further energy saving
At the same time, it is easy to control the film quality and uniform over a large area.
It is possible to obtain a crystalline deposited film with excellent film quality and characteristics.
Wear. Furthermore, it has excellent productivity and mass productivity, and is of high quality and electric.
A crystalline film with excellent physical properties such as physical, optical and semiconductor
Easy to get.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory view showing the relationship between the nucleus size r _c and the free energy G in the thin film formation process, and FIGS. 2 (A) and 2 (B) are explanations of the selective deposition method. 3 and 4 are graphs showing changes with time in the nucleation density (ND) between the SiI ₂ deposition surface and the silicon nitride deposition surface, and FIGS. 4A to 4D show the formation of crystals according to the present invention. FIG. 5 (A) and FIG. 5 (B) are perspective views corresponding to FIGS. 4 (A) and 4 (D), and FIGS. 6 (A) to 6 (D). ) Is a crystal forming process diagram showing a second embodiment of the present invention, and FIGS. 7A to 7D are formation process diagrams showing a third embodiment of a single crystal forming method according to the present invention. 8 (A) and (B) are perspective views corresponding to FIGS. 7 (A) and (D), and FIGS. 9 (A) to (D) are fourth embodiment examples of the present invention. Crystal 10A to 10C are formation process diagrams showing a fifth embodiment of the crystal formation method according to the present invention, and FIGS. 11A and 11B are Figure 10 (A) and (C)
FIGS. 12 (A) to 12 (C) are views showing a crystal forming process showing a sixth embodiment of the present invention, and FIGS. 13 (A) to 13 (C) are FIGS. 14A to 14D are schematic cross-sectional views showing an example of a multilayer structure manufactured by using the first embodiment of the present invention. FIGS. ) Is a diagram of a crystal forming process showing an eighth embodiment of the present invention. FIG. 16 is a diagram showing the relationship between the flow ratio of SiH ₄ and NH ₃ and the composition ratio of Si and N in the formed silicon nitride film. FIG. 17 is a graph showing the relationship between the Si / N composition ratio and the nucleation density, FIG. 18 is a graph showing the relationship between the Si ion implantation amount and the nucleation density, FIG. 19 ( FIGS. 20A to 20D are process diagrams showing a ninth embodiment of the method for forming a crystal according to the present invention. FIGS. 20A and 20B are diagrams in FIGS. 19A and 19D. Board FIGS. 21 (A) to 21 (D) are process charts for forming a crystal showing a tenth embodiment of the present invention, and FIGS. 22 (A) to 22 (D) are each a process for forming a single crystal according to the present invention. FIGS. 23 (A) and (B) are perspective views of the substrate in FIGS. 22 (A) and (D), and FIGS. 24 (A) to (C). ) Is a diagram of a crystal forming process showing a twelfth embodiment of the present invention. FIGS. 25 (A) and (B) are FIGS. 24 (A) and (C).
26 is a perspective view of the substrate in FIG. 26, FIGS. 26 (A) to 26 (D) are process diagrams of crystal formation showing the thirteenth embodiment of the present invention, and FIG. 27 is a schematic view of a film forming apparatus used in the embodiment of the present invention. It is a schematic diagram. FIG. 28 is a film forming process chart according to the present invention. FIG. 29 is another film forming step diagram according to the present invention. FIG. 30 is a schematic cross-sectional view showing an example of a deposited film obtained on a predetermined substrate by the method of the present invention, and FIG. 31 is a TFT made using the deposited film obtained by the method of the present invention. It is a schematic structural drawing. 101: deposition chamber 102: radical introduction pipe containing silicon and halogen 103: hydrogen radical introduction pipe 105: substrate 108, 108A: working chamber 109, 109A: outlet 110: roller 111: etching gas introduction pipe 113: working chamber 114: outlet 501: Substrate 502: Deposited film 601: Substrate 602: Semiconductor layer 603: Ohmic contact layer 604: Insulating layer 605: Contact all 606: Channel 607: Source metal electrode 608: Drain metal electrode 609: Gate metal electrode

Claims (1)

(57) [Claims] The active species (A) having Si ₂ F ₆ activated by the activation space (A) and the active species (B) having H ₂ activated by the activation space (B) are separately separated from each other by 10: 1 to At a flow ratio of 1:10, the non-nucleation surface (S _NDS ) having a low nucleation density and the non-nucleation surface (S _NDS ) having a sufficiently small area for crystal growth are formed.
_NDS nucleation density (ND _S ) greater than nucleation density (N
The nucleation surface (S _NDL ) having D _L ) is introduced into the film-forming space in which the substrate having the free surface adjacently arranged is placed and chemically reacted with the nucleation surface (S _NDL ) on the substrate. _NDL )
A method for forming a crystalline deposited film, which comprises forming a single nucleus in the substrate and growing a single crystal from the nucleus. 2. The nucleation surface (S _NDL ) is the non-nucleation surface (S _NDS )
Claims (1) in which a plurality of compartments are arranged inside
Item 14. The method for forming a crystalline deposited film according to item 4. 3. The nucleation surface (S _NDL ) is the non-nucleation surface (S _NDS )
The method for forming a crystalline deposited film according to claim (1), wherein a plurality of the regularly deposited layers are arranged. 4. The nucleation surface (S _NDL ) is the non-nucleation surface (S _NDS )
The method for forming a crystalline deposited film according to claim (1), wherein a plurality of irregularly partitioned areas are arranged. 5. The nucleation surface (S _NDL ) is the non-nucleation surface (S _NDS )
Claims (1) in which a plurality of compartments are divided and arranged above.
Item 14. The method for forming a crystalline deposited film according to item 4. 6. The nucleation surface (S _NDL ) is the non-nucleation surface (S _NDS )
The method for forming a crystalline deposited film according to claim (1), wherein a plurality of the regularly-divided partitions are arranged. 7. The nucleation surface (S _NDL ) is the non-nucleation surface (S _NDS )
The method for forming a crystalline deposited film according to claim (1), wherein a plurality of them are irregularly partitioned and arranged on the top. 8. The nucleation surface (S _NDL ) is the non-nucleation surface (S _NDS )
The method for forming a crystalline deposited film according to claim 1, wherein the material for forming is formed of a modified material. 9. The nucleation surface (S _NDL ) is the non-nucleation surface (S _NDS )
The method for forming a crystalline deposited film according to claim 1, wherein the crystalline deposited film is formed of a material different from a material for forming. 10. The method for forming a crystalline deposited film according to claim (1), wherein the non-nucleation surface (S _NDS ) is formed of an amorphous material. 11. Formation of the nucleation surface (S _NDL) by partitioning the provided plurality, than s husband nucleation surface (S _NDL), crystalline deposited film according to claim subsection (1) of claims of growing a single crystal Method. 12. Nucleation surface of said respective (S _NDL) respective nucleation surface a single crystal grown from (S _NDL) direction nucleation surface (S _NDL) ranges second (11) section of claims of growing beyond The method for forming a crystalline deposited film according to the above. 13. The method for forming a crystalline deposited film according to claim (11), wherein single crystals grown from each nucleation surface (S _NDL ) are grown to a size adjacent to each other between adjacent nucleation surfaces S _NDL ). 14． 3. The method according to claim 1, wherein the nucleation surface (S _NDL ) is formed by an ion implantation method.