JPH06310493A - Manufacturing equipment for semiconductor device - Google Patents

Abstract

PURPOSE:To make it possible to form an insulating film excellent in step coverage, flatness and quality that is suitable for use as insulating films in submicron devices and free from cracks and void. CONSTITUTION:The title equipment consists of a transporting means 4 for continuously conveying semiconductor substrates, and a plurality of processing chambers 1, 2 and 3 for treating the surfaces of semiconductor substrates, positioned along the transport path of the transporting means 4. Of these processing chambers at least an upstream one is used for processing organic compounds, and the remainder are for forming insulating films by thermal CVD. This continuously performs organic compound processing and CVD insulating film formation, and does not involve the degradation in throughput in processing organic compounds; therefore, the equipment is efficient.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor device manufacturing apparatus, particularly a primary insulating film provided between a semiconductor substrate and a first wiring layer, an interlayer insulating film provided between multilayer wiring layers, A semiconductor device in which a final insulating film acting as a passivation film, an insulating film such as a metal wiring or a sidewall of a gate electrode is formed by chemical vapor deposition (CVD) using an organic silicon compound or an inorganic silicon compound as a source gas The present invention relates to a manufacturing device.

[0002]

2. Description of the Related Art In recent years, high integration and high density of VLSI devices have been rapidly advanced, and submicron processing has become essential in semiconductor processing technology. As the submicron processing progresses, the unevenness of the semiconductor substrate surface becomes more and more intense,
The aspect ratio becomes large, and this unevenness becomes a constraint in device manufacturing. What is most strongly desired for solving such a problem is a technique for flattening an interlayer insulating film formed between multi-layer metal wirings.

Characteristics required for an interlayer insulating film for submicron devices include forming a space on the order of submicron and realizing excellent step coverage for a pattern having a high aspect ratio of 1 or more. . A chemical vapor deposition method (CVD method) using organic silane and inorganic silane as source gases is known as a method for forming an interlayer insulating film that satisfies such requirements. Also, CV
As the D method, plasma CVD method, atmospheric pressure CVD method, low pressure CVD method
Methods, pressure CVD method, photo-excited CVD method, etc. have been proposed.

Of these, an organic silane compound is used as a raw material gas, and ozone gas is added as a reaction gas to this at atmospheric pressure.
The insulating film formed by the CVD method, that is, the atmospheric pressure ozone-organosilane CVD silicon oxide film is one of the most expected methods because of its excellent flatness. An atmospheric pressure CVD method using such a mixed gas of ozone and an organic silane compound as a raw material gas is disclosed in, for example, JP-A-61-77695.
No. 7 (1988), pages 527 to 532, etc. Further, as the organosilane compound
TEOS (tetraethoxysilane), OMCTS (octamethylcyclotetr
asiloxane), HMDS (hexamethyldisiloxane), SOB (trimet
hylsilyl borate), DADBS (diacetoxyditertiary-butoxy
Known are silane) and SOP (trimethysilyl phosphate).

Further, in the insulating film used as the final protective film of the semiconductor device, the flatness and the film quality which influences the reliability of the element are strongly improved due to the higher integration and higher density of the VLSI device. Is required. This is mainly to prevent intrusion of moisture and the like from the outside of the element.

However, in the method of forming an insulating film by a CVD method using an organic silane compound as a raw material gas, the film formation rate and film quality are largely dependent on the underlying layer, resulting in poor step coverage and generation of voids. There is. For example, when forming an interlayer insulating film, the film forming speed on the underlying insulating film is slow, the film forming speed on the aluminum wiring is fast, and the wraparound between the wirings is small, so that the space between the wirings is not filled. As a result of the upper part being blocked, a large void is formed between aluminum wirings. Thus, the fact that a CVD film using an organic silane compound as a source gas has a large base dependency is described in, for example, JP-A-61-776.
No. 95 bulletin and "The Institute of Electrical Engineers of Japan A" published in 1991,
111, No. 7, pp. 652-658. When the voids are formed in this way, cracks occur in the interlayer insulating film, the leak current between the wirings increases, and the space between the wirings changes due to stress, which adversely affects the element characteristics.

The above-mentioned organic silane-based compound is used as a source gas, and ozone gas is added as a reaction gas to this to perform atmospheric pressure CVD.
A method of changing the ozone concentration from a low concentration to a high concentration in the process of forming an insulating film having a predetermined thickness is considered in order to reduce the dependency of the insulating film formed by the method on the underlayer. As a device for carrying out the above, a plurality of CVD film forming chambers capable of individually controlling film forming conditions are arranged along the transfer line of the semiconductor wafer, and the semiconductor wafer is continuously transferred while the initial film formation is performed. In the film forming chamber where the film is formed, low-concentration ozone conditions are used, and in the film forming chamber where the film forming is performed thereafter, the film is formed under high-concentration ozone conditions.
An apparatus for forming a CVD silicon oxide film is known.

[0008]

However, in the above-described film forming method and apparatus, the obtained atmospheric pressure ozone-organosilane was obtained.
Although it has become possible to avoid the occurrence of voids in the CVD silicon oxide film, it not only leaves the problem of poor filling between wiring steps with high aspect ratio, but also avoids the occurrence of such voids. For this reason, it is necessary to form a film with a thickness of at least 1000Å under low-concentration ozone conditions, while forming a film under such low-concentration ozone conditions requires a large amount of carbon containing water etc. Since the compound (unreacted material) is mixed in, the film quality in the entire film thickness is deteriorated as a result, and there are drawbacks that the moisture absorption resistance is poor and cracks are generated. Moisture in the film is due to via poisoning, deterioration of corrosion resistance of Al wiring corrosion hot carriers,
This causes an increase in dielectric constant (delay of signal) and the like.

The present invention solves the above-mentioned various drawbacks of the prior art and is excellent in step coverage and flatness,
In particular, it is possible to form an insulating film that is effective as an insulating film for submicron devices, has excellent film quality, and is free from cracks and voids. Therefore, a highly reliable semiconductor device can be manufactured. It is an object of the present invention to propose a semiconductor device manufacturing apparatus capable of achieving the above.

[0010]

A semiconductor device manufacturing apparatus according to the present invention comprises a carrier means for continuously transferring a semiconductor substrate, and a plurality of semiconductor substrates are subjected to surface treatment along a transfer path by the carrier means. Of the processing chamber, wherein at least one of the processing chambers on the upstream side of the transfer path is a processing chamber for performing an organic compound treatment,
The remainder is a processing chamber in which an insulating film is formed by thermal CVD.

Here, as the organic compound treatment,
Examples include exposure treatment of organic compounds, curtain flow coating treatment of organic compounds, and spray coating treatment of organic compounds.

When the insulating film is formed by thermal CVD according to the present invention, an organic silicon compound is used as a raw material,
Any of the inorganic silicon compounds can be used, and further, the boron compound and / or the phosphorus compound can be used together as a raw material.

[0013]

According to the semiconductor device manufacturing apparatus of the present invention as described above, the organic compound treatment can be performed on the underlying surface of the semiconductor wafer on which the insulating film is formed by chemical vapor deposition. Substrate dependence is greatly reduced. Therefore, the step filling property and the flatness are excellent, and no void is generated. Further, since the thickness of the insulating film formed can be reduced or eliminated under the condition of low ozone concentration, an insulating film having a good film quality containing very little water can be formed.

Further, in the apparatus of the present invention, by arranging a plurality of processing chambers on the same transfer means, the organic compound processing and the insulating film forming processing by the CVD method can be continuously performed. . Therefore, it is possible to process the organic compound without lowering the throughput, which is not only efficient, but also unlikely to have particles or dust attached during the transportation process, which improves the device characteristics and improves the yield. You can

Further, by disposing a plurality of processing chambers for forming an insulating film by thermal CVD after the organic compound processing, different kinds of insulating films can be formed in the respective processing chambers. For example, an atmospheric pressure ozone-organosilane CVD silicon oxide film can be formed in the upstream processing chamber, and an oxide film containing boron and / or phosphorus can be formed in the next processing chamber.

In the present invention, the organic compound used for the treatment with an organic compound is an aliphatic saturated monohydric alcohol, an aliphatic unsaturated monohydric alcohol, an aromatic alcohol,
One or more selected from aliphatic saturated polyhydric alcohols, aldehydes, ethers, ketones, carboxylic acids, nitroalkanes, amines, acyl nitrites, acid amides, and heterocyclic compounds can be mentioned. Such substances can be used.

Aliphatic saturated monohydric alcohols: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol,
2-butanol, 2-methyl-2-propanol, 1-
Pentanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 1
-Hexanol, cyclohexanol

Aliphatic unsaturated monohydric alcohols: allyl alcohol, propargyl alcohol, 2-methyl-3-butyn-2-ol

Aromatic alcohols: benzyl alcohol, furfuryl alcohol

Aliphatic saturated polyhydric alcohols and their derivatives: ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, propylene glycol monomethyl ether, Ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether

Aldehydes: formaldehyde, acetaldehyde, glyoxal

Ether: Diethyl ether, dioxane, tetrahydrofuran, tetrahydrofurfuryl alcohol

Ketone / keto alcohol: acetone, 2-
Butanone, diacetone alcohol, γ-butyrolactone,
Propylene carbonate

Carboxylic acid: formic acid, acetic acid, propionic acid,
Glycolic acid, lactic acid, ethyl lactate

Nitroalkane: nitromethane, nitroethane, nitropropane, nitrobenzene

Amine: ethylamine, propylamine,
Isopropylamine, butylamine, isobutylamine, allylamine, aniline, toluidine, ethylenediamine, diethylamine, ethyleneimine, dipropylamine, diisopropylamine, dibutylamine, triethylamine, tri-n-propylamine, tri-n-butylamine

Acyl nitriles: acetonitrile, propiononitrile, butyronitrile, acrylonitrile,
Methacrylonitrile, benzonitrile

Acid amide: formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide,

Heterocyclic compounds: pyridine, quinoline, pyrrole, piperidine, piperazine, morpholine, 2-pyrrolidinone, 1-methyl-2-pyrrolidinone

In the present invention, one kind of such organic compound may be subjected to a base treatment, or two or more kinds of organic compounds may be simultaneously or sequentially treated.

Further, as the treatment of the organic substance on the surface of the base, a vapor treatment of spraying a vapor of an organic compound onto a semiconductor wafer is representative, but in addition to this, a spray treatment for spraying a solution of the organic compound, a semiconductor for a liquid film of the organic compound. A curtain flow coating process or the like in which the substrate is passed is possible, and any of them can be easily performed.

Although the reason why an insulating film having a good film quality with a good filling property between the steps is formed by treating the underlying surface with an organic substance has not been clarified yet,
The following can be considered as an example of the case where the underlayer surface of the O ₃ -TEOS CVD NSG (Non-doped silicon glass) film is treated with an organic substance.

1. SiH ₄ or TEOS-based plasma CVD oxide film, thermal CVD oxide film, or Si thermal oxide film used as a modified insulating film by ethanol treatment on the surface of the underlying insulating film is a composition similar to amorphous SiO ₂ or SiO _2. belongs to. The outermost surface of amorphous SiO ₂ is often hydrated by water in the process or in the air atmosphere, and often has a silanol type structure of Si—OH. Si-OH existing on the surface
Is an electron attracted to the Si side, which has a high electronegativity, so

[Chemical 1] It is strongly polarized in the form of and has a large dipole moment. Due to this polarization, Si-OH has the property of strongly adsorbing highly polar molecules such as water and alcohol. An important application that maximizes the Si-OH adsorption capacity by increasing the specific surface area is silica gel as a desiccant.

It is assumed that a gaseous organic compound is sprayed or a liquid organic compound is applied or dipped on the SiO ₂ insulating film whose surface is covered with Si—OH to act. Many organic compounds are adsorbed on the surface by the action of the polarization of Si-OH, but the strength of the adsorption depends on the polarity of the organic compound side. Non-polar substances such as cyclohexane and benzene are difficult to be adsorbed on the surface, and highly polar substances such as lower alcohol, acetonitrile and lower carboxylic acid are strongly adsorbed. Dioxane and ketones with moderate polarity are expected to be adsorbed with intermediate strength.

On the other hand, Si-OH is a proton-releasing Lewis.
It also acts as an acid and interacts with other active hydroxyl-bearing organic chemicals. A typical example is the exchange reaction of an alkoxyl group that occurs with an alcohol. For example, in the case of ethanol: C ₂ H ₅ OH, Si-OH + C ₂ H ₅ OH = Si-OC ₂ H ₅ + H ₂ O Such an esterification reaction occurs. Si formed here
The bond of -OC ₂ H ₅ is extremely strong, and Si-OC ₂ H ₅ formed on the native oxide film of Si has a life of several tens of minutes or more even in an oxidizing atmosphere at 400 ° C.

Therefore, it is considered that the gas phase or liquid phase treatment with the organic compound causes the chemical adsorption of the organic compound molecule, and the treatment with the alcohol such as ethanol also causes the esterification reaction. In any case, the silanol thus adsorbed or esterified loses its adsorbing ability and becomes an inactive surface state. To evaluate the degree of adsorption on the surface of the insulating film, the desorption temperature of the adsorbed chemical species should be used as a guide, and the tendency tends to be the same as the polarity of the adsorbed chemical species. Shows a particularly high desorption temperature.

2. O ₃ -TEOS system vapor-phase chemical reaction and vapor deposition chemical species in vapor phase In the thermal CVD reaction of O ₃ -TEOS, two intermediate chemical substances (deposition chemical species) that contribute to film formation are formed in the vapor phase. It is said to exist. One having a silanol group: HO-Si (OC ₂ H ₅ ).
₃ (A), it is considered that TEOS (Si (OC ₂ H ₅ ) ₄ ) and atomic oxygen [O] are chemically formed as follows. Note that TE
OS and O ₃ do not react directly with each other, and the initiation of the reaction is said to occur from atomic oxygen [O] generated by thermal decomposition of O ₃ .

[Chemical 2] That is, this is a reaction in which an ethoxy group bonded to Si is oxidized by an oxygen atom and decomposed to leave silanol.
In equation (1), the final oxidation products were CO ₂ and H ₂ O.
Actually, as an intermediate step, ethanol (C ₂ H ₅ OH),
Methanol (CH ₃ OH), acetaldehyde (CH ₃ CHO),
Formaldehyde (HCHO), acetic acid (CH ₃ COOH), it is believed that through the formic acid (HCOOH).

Another intermediate is a siloxane polymer:
_{(C 2 H 5 O) 3} Si-O-Si (OC 2 H 5) is ₃ (B). This is above
It is considered that the silanol intermediate (A) produced by the formula (1) is condensed to form a reaction such as (2) or (2 ').

[Chemical 3] Since the lifetime of silanol in the gas phase is generally considered to be short, the silanol intermediate (A) has a relatively short life, (2),
It is considered that the siloxane polymer (B) is easily transformed by the condensation reaction such as (2 ').

[Chemical 4]

The silanol intermediate (A) is active in the molecule.
Since it has a Si-OH group, it has high activity and is easy to polymerize. In addition, it has a large intramolecular polarization and is easily adsorbed to the substrate surface. On the other hand, siloxane intermediate (B)
Has a low activity, and since it has a high boiling point and a low vapor pressure, it is highly possible that it is in a liquid state at about the film formation temperature. Since the polarization is small, it is considered that adsorption is difficult.

Therefore, in the mechanism in which the silanol intermediate (A) mainly contributes to the film formation, the adsorption of (A) to the substrate surface occurs rapidly, and then the ethoxy groups remaining in the adsorbed molecules are ozone-oxidized. Polysilanol (Si (OH)
_n , n> 1), and the silanol thus produced becomes a new adsorption site, and the film-forming species (A) in the gas phase is adsorbed again there (adsorption-decomposition mechanism). Since (A) is reactive, the lifetime of the intermediate is short, the sticking coefficient is large, and the adsorption of (A) to the easily-supplied site occurs at a high speed, which deteriorates the step coverage. Moreover, since the probability that silanol remains in the film as it is increases, the film quality and its uniformity are relatively poor, and the amount of water adsorbed on the surface tends to be large.

In contrast to this, when the siloxane polymer intermediate (B) mainly contributes to film formation, adsorption is unlikely to occur, and therefore diffusion (fluidity) due to interfacial tension of the polymer onto the substrate surface causes film formation. It is considered to control. The polymer that has spread to the surface undergoes silanolization and polymerization by ozone oxidation again, but since the free silanol density that appears on the surface is considered to be small, it is considered that the film-forming species (B) in the gas phase is deposited again in a fluidized state. Possible (polymerization-flow mechanism). Since the intermediate (B) has a long lifetime, the step coverage is increased and the shape is flow-like. Since the residual silanols on the surface and inside the film are reduced, the film quality is relatively improved.

Regardless of whether the intermediates (A) and (B) are predominant, the chemical species deposited by heat or excess ozone are finally decomposed and oxidized to form a Si-O-Si network. , Close to stoichiometric amorphous SiO ₂ . However, it is considered that only one of (A) and (B) is involved in film formation, and it is considered that two chemical species are always involved in film formation. It is considered that the balance involved in the film formation of (A) and (B) changes depending on the parameters and the surface condition of the base.

3. Relationship between Surface State of Underlayer and Chemical Reaction in Gas Phase As is clear from the explanation of the above mechanism, it is understood that the shape after film formation is greatly changed depending on the balance of film forming chemical species in the gas phase. When Si-OH adsorption sites are distributed at a high density on the substrate, silanol intermediate (A) among the chemical species in the gas phase is adsorbed on the surface immediately without waiting for the polymerization reaction due to its large polarization. It is considered to be a thing. The adsorbed silanol is immediately oxidised by ozone or heat to produce silanol which can become a new adsorption site, or is adducted by another silanol intermediate (A). Film deposition by various adsorption-decomposition mechanisms continues to proceed. The deposition of the siloxane polymer (B) is also considered to proceed in parallel with that of (A), although the proportion is small, and the local fluctuation of the film quality occurs due to the mixture of the two film forming species, which causes unevenness when etching with BHF. May be the cause of. We believe that this type is the mechanism of O ₃ -TEOS film formation on the oxide film not treated with ethanol.

When the underlayer insulating film is treated with an organic compound and all the adsorbing active silanol is crushed, the silanol intermediate (A) is not adsorbed on the substrate. Therefore, the residence time in the gas phase increases and the probability of conversion to the siloxane polymer (B) increases, so that the proportion of (B) in the film formation chemical species in the gas phase increases. The siloxane polymer (B) spreads so as to cover the substrate surface with interfacial tension. This polymer has no active silanols, so once the membrane surface is covered with (B), the silanol intermediate (A)
Will not be adsorbed thereafter, and the subsequent deposition will proceed mainly by the flow of the siloxane polymer (B).

That is, the state of the substrate before film formation can have a decisive influence on the film formation mechanism after film formation.
The pretreatment of film formation with an organic compound is inferred from the above mechanism, and if it is a compound that is not desorbed at a film forming temperature of about 400 ° C, a complete effect can be obtained if it is adsorbed on all active adsorption sites. Any of these may be used, but acetonitrile having a high polarity and lower alcohol having an esterification action remain stable without being desorbed even at this film forming temperature, and are considered to be the most suitable ones.

However, in the earliest process in which the siloxane polymer flows due to the interfacial tension, the absolute value of the interfacial tension between the polymer and the substrate surface is likely to affect the final flow shape. That is, the wettability between the polymer and the treated substrate becomes a problem, and it is desirable to adsorb or esterify the chemical species that are well wetted by the polymer by the treatment of the organic compound in order to obtain a good flow shape. That is why the treatment with ethanol or 2-ethoxyethanol, which has the same functional groups as the polymer, actually gives favorable results.

Although the above description is based on the results of theory and experiment, it is only an inference, and it goes without saying that the technical scope of the present invention is not limited by such inference.

As the silicon compound for performing chemical vapor deposition in the processing chamber for forming the insulating film after the organic compound processing, either an organic silicon compound or an inorganic silicon compound may be used. As organic silicon compounds, TEOS, TMOS,
The following organosilicon compounds are listed as representative examples of OMTCS, HMDS, SOB, DADBS, SOP and the like.

The tetraalkoxysilanes are as follows: tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetra-n-propoxysilane, tetra-isopropoxy-silane, tetra-n-butoxy-silane.

Alkylalkoxysilanes are as follows: methyltrimethoxysilane, methyltriethoxysilane, methyltrinpropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrinpropoxysilane,
Ethyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, methyl Vinyldimethoxysilane, methylvinyldiethoxysilane methyldimethoxysilane, methyldiethoxysilane dimethylvinylmethoxysilane, dimethylvinylethoxysilane

As polysiloxane: tetrakis (dimethylsiloxy) silane

The cyclosiloxanes are as follows: Octamethylcyclotetrasiloxane (OMCTS), pentamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, trimethylcyclotrisiloxane.

The disiloxanes are as follows: hexamethyldisiloxane (HMDS), tetramethyldimethoxydisiloxane, dimethyltetramethoxydisiloxane, hexamethoxydisiloxane.

The following are alkylsilanes: monomethylsilane, dimethylsilane, trimethylsilane, triethylsilane, tetramethylsilane, tetraethylsilane allyltrimethylsilane hexamethyldisilane.

The silylamines are as follows: dimethyltrimethylsilylamine, diethyltrimethylsilylamine

The silane nitrogen derivatives are as follows: aminopropyltriethoxysilane, trimethylsilyl azide, trimethylsilyl cyanide

The silazanes are as follows: hexamethyldisilazane, tetramethyldisilazane octamethylcyclotetrasilazane, hexamethylcyclotrisilazane

The halogenated silanes and derivatives are as follows: trimethylchlorosilane, triethylchlorosilane, trinpropylchlorosilane, methyldichlorosilane, dimethylchlorosilane, chloromethyldimethylchlorosilane, chloromethyltrimethylsilane, chloropropylmethyldichlorosilane, chloropropyltrisilane. Methoxysilane dimethyldichlorosilane, diethyldichlorosilane, methylvinyldichlorosilane, methyltrichlorosilane,
Ethyltrichlorosilane, vinyltrichlorosilane, trifluoropropyltrichlorosilane, trifluoropropyltrimethoxysilane, trimethylsilyl iodide.

Further, as the organic silicon compound, tris (trimethylsiloxy) borane (SOB), tris (trimethylsiloxy) phosphoryl (SOP), diacetoxydi-t
ert-Butoxysilane (DADBS) or the like can also be used.

In the present invention, the above-mentioned organosilicon compounds may be used alone or two or more organosilicon compounds may be mixed and used. When mixed and used, the mixing ratio may be set appropriately.

Further, the inorganic silane is silane,
Representative examples are disilane, trisilane, and tetrasilane, and other examples thereof include chlorosilanes such as monochlorosilane, dichlorosilane, and trichlorosilane. These inorganic silanes can also be used in combination of two or more kinds.

In addition, during chemical vapor deposition using such an organic silicon compound or an inorganic silicon compound as a raw material, B and P raw materials such as diborane and phosphine are simultaneously supplied,
It is also possible to form a PSG film or a BPSG film.
The B and P raw materials are as follows. Compounds containing _{B: BH 3, B (CH} 3) 3, BH 2 CH 3, B (N (CH 3) 3)
_{3, B (OCH 3) 3} , B (OC 2 H 5) 3 , etc. Compounds containing _{P: PH 3, PO (OCH} 3) 3, (CH 3) 3 P, (CH 3) 3
Compounds containing PO or the like Si-B: B ((OSi (CH 3) 3) 3, (CH 3) 3 SiOB (C
H ₃₎ compound containing ₂ or the like Si-P: PO ((OSi (CH 3) 3) 3, P ((OSi (C
_{H 3) 3) 3, (} CH 3 O) POSi (OCH 3) 3, Si (OPO (OCH 3) 2) 4 , etc. Si-B-P a containing _{compound: PO ((OSi (CH 3} ) 3) 2 OSiOB (OCH ₃ )
₂ , POB (OSi (CH ₃ ) ₃ ) _3, etc. These compounds can also be mixed and used.

The raw material organic silicon compound or inorganic silicon compound is supplied to a bubbler heated to a constant temperature, bubbled with nitrogen, oxygen, helium or the like as a carrier gas and transported to a film forming chamber. It is desirable to heat the piping after bubbling to prevent condensation. As the reaction gas, an oxygen gas containing oxygen or ozone at a concentration of 0.1 wt% or more, preferably 4 wt% or more is used. Further, it is possible to appropriately dilute with an inert gas such as nitrogen. The flow ratio of these organic silicon compound, inorganic silicon compound, reaction gas and carrier gas is not particularly limited. Insulation film deposition temperature is 200-500 ℃, preferably 300-450 ℃
Is.

[0064]

FIG. 1 schematically shows an embodiment of the semiconductor device manufacturing apparatus of the present invention. In the apparatus of this embodiment, a total of three treatments of a first treatment chamber 1, a second treatment chamber 2 and a third treatment chamber 3 for performing an organic compound treatment or an insulating film forming treatment on a semiconductor wafer are performed. It has a room. Further, as a semiconductor wafer transfer means, a belt conveyor 4 wound around a plurality of rolls is provided, and the semiconductor wafer placed on the belt conveyor 4 is transferred from the left hand to the right hand of the paper. . The semiconductor wafer transfer line of the belt conveyor 4 is provided inside a housing (not shown) in order to prevent adhesion of dust and the like.

The first processing chamber 1, the second processing chamber 2 and the third processing chamber 3 are arranged along the semiconductor wafer transfer line of the belt conveyor 4, and in this line. While introducing the inert gas (N ₂ gas) between the processing chambers, the gas in each processing chamber is mixed into the other processing chambers by exhausting the gas from the exhaust ports 5 on both sides of each processing chamber. This allows each processing chamber to carry out individual processing. Exhaust ports 6 are also provided at both ends of the semiconductor wafer transfer line. 7 is a manometer.

First processing chamber 1, second processing chamber 2 and third processing chamber
By arranging the processing chambers 3 at equal intervals, it is possible to simultaneously process a plurality of semiconductor wafers in each processing chamber. The semiconductor wafer can be conveyed by the belt conveyor 4 by stopping the feeding when the semiconductor wafer enters each processing chamber or by intermittent feeding, but it is common to perform each processing while continuously conveying the semiconductor wafer. Is.
The processing time and the film formation time can be changed depending on the transport speed.

At a position away from the semiconductor wafer transfer line, the belt of the belt conveyor 4 is washed to remove particles and the like adhering to the belt surface due to film formation or the like. For that purpose, an ultrasonic belt cleaner 8 which is immersed in a cleaning solution for cleaning and a belt cleaner 9 which is cleaned with hydrofluoric acid (HF) gas are provided. Note that 10 is a dryer.

FIG. 2 shows a plan view of the main part of the apparatus shown in FIG. In the case where there are three processing chambers as shown in this figure, the combination of the organic compound treatment and the insulating film forming treatment by chemical vapor deposition is performed by using the first treatment chamber 1 for the treatment of the organic compound and the second treatment chamber. It is preferable that the second and third processing chambers 3 are subjected to an insulating film forming process.

As the organic compound treatment performed in the first processing chamber 1, exposure treatment of an organic compound, curtain flow coating treatment of an organic compound, spray coating treatment of an organic compound is suitable. As shown in FIG. An example of the apparatus for performing a process is shown. This device includes an injector 11 for blowing a gas of an organic compound onto a semiconductor wafer,
The exhaust assembly 12 for discharging the raw material gas after spraying and the nitrogen gas for shielding, and the screen 13 for guiding the shielding nitrogen gas to the exhaust assembly without disturbance are mounted on the belt 4. The organic compound gas or its dilution gas guided to the injector 11 is sprayed from the slit-shaped gap to the semiconductor wafer 11 that moves continuously while being placed. In the case where the heating temperature difference of the semiconductor substrate becomes a problem between the organic compound treatment and the subsequent insulating film forming treatment, the semiconductor substrate may be heated by heating up in consideration of the temperature decrease due to the treatment. Good. Further, when the semiconductor substrate reaches between the first processing chamber (50 ° C.) and the second processing chamber (300 to 500 ° C.), the transfer speed is reduced to preheat it for several seconds.

Next, FIG. 4 shows a three-dimensional exploded view of the components inside the second processing chamber 2, but the same applies to the third processing chamber.
Reference numeral 21 in the figure denotes an injector, which guides various raw material gases directed to the semiconductor wafer together with a carrier gas to blow them. 22 is an exhaust assembly, which is an injector
The raw material gas blown from 21 onto the semiconductor wafer, the shielding nitrogen gas, and the generated particles are discharged to the outside, and are connected to a discharge conduit (not shown). Reference numeral 23 denotes a shield, which has a slit gap for guiding the source gas from the injector 21 in the central portion and is arranged to face the surface of the semiconductor wafer. The shield 23 prevents particles from adhering to the injector 21 and the exhaust assembly 22 and guides the shielding nitrogen gas to the exhaust assembly without disturbance.

Examples of the insulating film forming process in the second processing chamber 2 and the third processing chamber 3 are the second processing chamber and the third processing chamber.
Atmospheric pressure ozone-organosilane CV
The second processing chamber where the formation of the DNSG film is performed at a low ozone concentration in the second processing chamber and the third processing chamber is at a high ozone concentration, and the atmospheric pressure ozone-organosilane CVD NSG film is formed. In the second process, the atmospheric pressure ozone-organic silane CVD NSG film is formed. In the third processing chamber, the boron compound and / or phosphorus compound is also used as the raw material to form the PSG film and the BPSG film. Atmospheric pressure ozone in the processing room-Organosilane CV
There is a process of forming a D NSG film and a process of forming a normal pressure-inorganic silane CVD NSG film in the third processing chamber.

A concrete example of manufacturing a semiconductor device using the above-described semiconductor device manufacturing apparatus will be described below. Example 1 As shown in FIG. 5, a thermal oxide film 32 is formed on a semiconductor substrate 31.
After forming 0.1 μm and then forming a polysilicon film to 0.5 μm, the polysilicon film is selectively etched to obtain a pattern width of 0.5 μm and a space width of 0.5 μm.
Polysilicon wiring 33 of was formed. Next, a thermal oxide film 34 having a thickness of 300 Å was formed on the thermal oxide film 32 and the polysilicon wiring 33, and then the semiconductor wafer was carried into the semiconductor manufacturing apparatus of the present invention shown in FIGS. The conveyor speed of this semiconductor manufacturing equipment is 75 mm / min, and the preheating section is 50 mm.
/ min.

In the first processing chamber 1, ethanol gas was introduced and sprayed onto the injector 11 as an organic compound treatment. This ethanol gas is generated by accommodating an ethanol liquid in a gas bubbler connected to the injector 11, supplying nitrogen gas as a carrier gas to this gas bubbler at 1.0 SLM, and bubbling at a bubbling temperature of about 50 ° C. is there. At this time, the concentration of ethanol gas guided to the injector 11 is 30%, and the substrate temperature is 50%.
C., the processing time was 1 minute.

Next, in the second processing chamber, normal pressure -O ₃ TEOS NS
A G film was formed. This film formation was carried out by introducing a mixed gas of TEOS gas and ozone gas into the injector 21 as a raw material gas by chemical vapor deposition and spraying it onto the semiconductor wafer after the organic compound treatment. TEOS gas was generated by supplying nitrogen gas to the TEOS liquid contained in a gas bubbler in a constant temperature bath maintained at 65 ° C (TEOS flow rate 11.85 sccm). Ozone gas was generated at a rate of 144 mg / l by introducing oxygen gas into the ozonizer at a flow rate of 8.5 SLM. Furthermore, the substrate temperature is 40
The temperature was 0 ° C. The film deposition rate under these conditions is 1600Å / min
The film formation time is 2 minutes, and the film thickness is 3200Å at normal pressure -O _3.
A TEOS NSG film was formed.

Next, in the third processing chamber, the atmospheric pressure-O ₃ TEOS NSG film was formed under the same conditions as in the second processing chamber. Deposition time is 2 minutes and film thickness is 3200Å normal pressure-O ₃ TEOS NSG
The point that the film is formed is also the same. The film thickness thus obtained 64
The 00 Å normal pressure-O ₃ TEOS NSG film 35 was a film with good levelness because the steps were completely filled. Further, it was an insulating film of good film quality with no voids and little water content in the film.

Example 2 In this example, after an organic compound treatment, an atmospheric pressure-O ₃ TEOS NSG film is first formed as an insulating film, and then BPSG is used.
It is an example of generating a film. As shown in FIG. 6, the semiconductor substrate
A thermal oxide film 32 of 0.1 μm is formed on 31 and then a polysilicon film of 0.5 μm is formed, and then the polysilicon film is selectively etched to obtain a pattern width of 0.5 μm.
A polysilicon wiring 33 having a space of 0.5 μm and a space width of 0.5 μm was formed. Next, a thermal oxide film 34 having a thickness of 300 Å was formed on the thermal oxide film 32 and the polysilicon wiring 33, and then the semiconductor wafer was carried into the semiconductor manufacturing apparatus of the present invention shown in FIGS.
The conveyor speed of the belt conveyor 4 of this semiconductor manufacturing apparatus is 75
mm / min 50 mm / min in the preheating part.

In the first processing chamber 1, ethanol gas was introduced and sprayed onto the injector 11 as an organic compound treatment. This ethanol gas is generated by accommodating an ethanol liquid in a gas bubbler connected to the injector 11, supplying nitrogen gas as a carrier gas to the gas bubbler at 1.0 SLM and bubbling at a bubbling temperature of 50 ° C. . At this time, the concentration of ethanol gas guided to the injector 11 is 30%, and the substrate temperature is 50%.
C., the processing time was 1 minute. Next, in the second processing chamber, an atmospheric pressure-O ₃ TEOS NSG film was formed. This film is formed on the injector 21 by using TE as a source gas by chemical vapor deposition.
A mixed gas of OS gas and ozone gas was introduced and sprayed onto the semiconductor wafer after the organic compound treatment. TEOS gas was stored in a gas bubbler in a constant temperature bath maintained at 65 ° C.
It was generated by supplying nitrogen gas to the TEOS liquid (TEOS flow rate 11.8
5 sccm). Ozone gas was generated at a rate of 144 mg / l by introducing oxygen gas into the ozonizer at a flow rate of 8.5 SLM.
The substrate temperature was 400 ° C. The film forming rate under these conditions was 1600Å / min, and the film forming time was 1 minute to form a normal pressure -O ₃ TEOS NSG film 35 having a film thickness of 1600Å. Up to this point, the procedure is the same as in the first embodiment.

Next, in the third processing chamber, a BPSG film was formed. This film is formed by injector 21
TEOS gas and TMP (Trimethylphosphate) as raw material gas
A mixed gas of gas, TMB (Trimethylborate) gas and ozone gas was introduced and sprayed onto the semiconductor wafer after the organic compound treatment. TEOS gas was generated by supplying nitrogen gas to the TEOS liquid contained in a gas bubbler in a constant temperature bath maintained at 65 ° C (TEOS flow rate 11.85 sccm). TMP gas, TMB
Gas was also generated by supplying nitrogen gas to each of TMP liquid and TMB liquid contained in a gas bubbler in a constant temperature bath maintained at 65 ° C (TMP flow rate 1 sccm, TMB flow rate 3 sccm). For ozone gas, the flow rate of oxygen gas to the ozonizer is 8.5 SLM.
And was generated at a rate of 144 mg / l. The substrate temperature was 400 ° C. The deposition rate under these conditions is 1600
Å / min, the film formation time is 3 minutes, and the film thickness is 4800Å BP
The SG film 36 was formed.

The insulating film 35 having a film thickness of 6400Å thus obtained,
The film of No. 36 was a film in which the steps were completely buried and the flatness was good. In addition, there are no voids, and the water content in the film is low.
The insulating film had a good film quality.

Example 3 This example is an example in which after an organic compound treatment, an atmospheric pressure -O ₃ TEOS NSG film is first formed as an insulating film, and then an NSG film using inorganic silane as a raw material is formed. . As shown in FIG. 7, a thermal oxide film 32 of 0.1 μm is formed on the semiconductor substrate 31.
Then, a polysilicon film having a thickness of 0.5 μm and a polysilicon film 33 having a pattern width of 0.5 μm and a space width of 0.5 μm were formed by selectively etching the polysilicon film. Next, a thermal oxide film 34 having a thickness of 300 Å was formed on the thermal oxide film 32 and the polysilicon wiring 33, and then the semiconductor wafer was carried into the semiconductor manufacturing apparatus of the present invention shown in FIGS. The conveyor speed of this semiconductor manufacturing equipment is 75 mm / min, and the preheating section is 50 mm / m.
is in.

In the first processing chamber 1, ethanol gas was introduced and sprayed onto the injector 11 as an organic compound treatment. This ethanol gas is generated by accommodating an ethanol liquid in a gas bubbler connected to the injector 11, supplying nitrogen gas as a carrier gas to the gas bubbler at 1.0 SLM and bubbling at a bubbling temperature of 50 ° C. . At this time, the concentration of ethanol gas guided to the injector 11 is 30%, and the substrate temperature is 50%.
C., the processing time was 1 minute. Next, in the second processing chamber, the atmospheric pressure-O ₃ TEOS NSG film 35 was formed. This film is formed by chemical vapor deposition as a source gas on the injector 21.
A mixed gas of TEOS gas and ozone gas was introduced and sprayed on the semiconductor wafer after the organic compound treatment. TEOS gas was generated by supplying nitrogen gas to the TEOS liquid contained in a gas bubbler in a constant temperature bath maintained at 65 ° C (TEOS flow rate 1
1.85 sccm). Ozone gas was generated at a rate of 144 mg / l by introducing oxygen gas into the ozonizer at a flow rate of 8.5 SLM. The substrate temperature was 400 ° C. The film forming rate under these conditions was 1600Å / min, and the film forming time was 1 minute to form a normal pressure -O ₃ TEOS NSG film 35 having a film thickness of 1600Å. Up to this point, the procedure is the same as in the first embodiment.

Next, in the third processing chamber, an NSG film 37 made of inorganic silane, specifically SiH ₄ , was formed. This film formation was performed by introducing a mixed gas of SiH ₄ gas and oxygen gas into the injector 21 as a raw material gas by chemical vapor deposition and spraying the mixed gas on the semiconductor wafer after the organic compound treatment. Si
The H ₄ gas flow rate was 400 sccm as the gas flow rate of SiH ₄ diluted with nitrogen gas to 4%, the oxygen gas flow rate was 500 sccm, and the nitrogen gas was 5 SLM as the dilution gas. The substrate temperature was 400 ° C. The film deposition rate under these conditions is 20
It was 00Å / min and the film formation time was 3 minutes to form a normal pressure -O ₂ SiH ₄ NSG film 37 having a film thickness of 6000Å. Thus obtained insulating films 35 and 37 having a film thickness of 7600Å were films with good flatness because the steps were completely buried. Further, it was an insulating film of good film quality with no voids and little water content in the film.

Next, as a comparative example, an example will be described in which the insulating film is formed in the first reaction chamber but no organic compound is applied. As shown in FIG. 8, a thermal oxide film 32 having a thickness of 0.1 μm is formed on the semiconductor substrate 31, and then a polysilicon film having a thickness of 0.5 μm is formed.
After the formation of μm, the polysilicon film is selectively etched to obtain a pattern width of 0.5 μm and a space width.
A 0.5 μm polysilicon wiring 33 was formed. Next, a thermal oxide film 34 having a thickness of 30 is formed on the thermal oxide film 32 and the polysilicon wiring 33.
After being formed with 0Å, the semiconductor wafer was carried into the semiconductor manufacturing apparatus of the present invention shown in FIGS. The conveyance speed of the belt conveyor 4 of this semiconductor manufacturing apparatus is mm / min. Up to this point, the procedure is the same as in the first embodiment.

Next, in the first processing chamber 1, normal pressure -O ₃ TEO
A S NSG film was formed. This film is formed by chemical vapor deposition,
A mixed gas of TEOS gas and ozone gas was introduced to the injector 21 as a raw material gas and sprayed onto the semiconductor wafer after the organic compound treatment. TEOS gas was generated by supplying nitrogen gas to the TEOS liquid contained in a gas bubbler in a constant temperature bath maintained at 65 ° C (TEOS flow rate 11.85 sccm). Ozone gas was generated at a rate of 144 mg / l by introducing oxygen gas into the ozonizer at a flow rate of 8.5 SLM. Furthermore, the substrate temperature is
The temperature was 400 ° C. The deposition rate under these conditions is 1600Å / m
in, the film formation time is 1 minute, and the film thickness is 1600Å at normal pressure-
An O ₃ TEOS NSG film was formed.

Next, also in the second and third processing chambers, the atmospheric pressure is -O ₃ T.
An EOS NSG film was formed. This film formation is the same as in the first processing chamber, and the film formation time is 2 minutes each, and the film thickness is 4 minutes in total.
6400Å normal pressure-O ₃ TEOS NSG film was formed. In the thus-obtained normal pressure -O ₃ TEOS NSG film 35 having a film thickness of 8000 Å, the underlayer dependence was clearly recognized and the flatness was poor. Further, not only voids and keyholes were generated, but the water content in the film was more than an order of magnitude higher than in the examples.

The present invention is not limited to the above-mentioned embodiments, but various modifications can be made. For example, the number of processing chambers provided in the semiconductor device manufacturing apparatus of the present invention may be at least one for each of the organic compound processing chamber and the film-forming processing chamber, and a total of four or more. It doesn't matter. Further, the processing chamber for the organic compound is not limited to the most upstream side in the semiconductor substrate transfer line. For example, after forming an insulating film by chemical vapor deposition using organic silane or inorganic silane as a raw material, the second and subsequent organic compounds are counted from the upstream side of the transport line in order to process the organic compound. A processing chamber may be provided. Further, the number of processing chambers for performing the organic compound processing may be at least one, but may be two or more. In addition, the means for transporting the semiconductor wafer is not limited to the belt conveyor, and any means capable of continuously transporting the semiconductor wafer can be used.

[0087]

The semiconductor device manufacturing apparatus according to the present invention comprises a transfer means for continuously transferring the semiconductor substrate, and includes a plurality of processing chambers for subjecting the semiconductor substrate to surface treatment along the transfer path by the transfer means. Among them, at least one on the upstream side of the transfer path is a processing chamber for performing an organic compound treatment, and the rest is a processing chamber for forming an insulating film by thermal CVD, thereby forming an insulating film by chemical vapor deposition. Since the surface can be treated with an organic compound, the dependency of the insulating film on the underlying layer can be greatly reduced, and in addition, the step filling property and the flatness are excellent, and void-free insulation is achieved. A membrane can be obtained. Further, the apparatus of the present invention can perform the organic compound treatment and the insulating film formation treatment by the CVD method continuously, so that efficient treatment is possible.

[Brief description of drawings]

FIG. 1 is a schematic view showing an embodiment of a semiconductor device manufacturing apparatus of the present invention.

FIG. 2 is a plan view of an essential part of the semiconductor device manufacturing apparatus of the present invention shown in FIG.

FIG. 3 is a cross-sectional view showing an example of an apparatus for performing an exposure treatment of an organic compound.

FIG. 4 is a three-dimensional exploded view of components in the second processing chamber.

FIG. 5 is a sectional view showing a semiconductor device formed by an embodiment of a semiconductor device manufacturing apparatus according to the present invention.

FIG. 6 is a cross-sectional view showing a semiconductor device formed by another embodiment of the semiconductor device manufacturing apparatus of the present invention.

FIG. 7 is a cross-sectional view showing a semiconductor device formed by another embodiment of the semiconductor device manufacturing apparatus of the present invention.

FIG. 8 is a cross-sectional view showing a semiconductor device formed according to a comparative example that does not use the semiconductor device manufacturing apparatus of the present invention.

[Explanation of symbols]

 1 1st processing chamber 2 2nd processing chamber 3 3rd processing chamber 4 Belt conveyor

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Yohta Ota, 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Prefecture Technical Research Division, Kawasaki Steel Co., Ltd. (72) Osamu Tomoda Kawasaki-cho, Chiba-ku, Chiba-shi No. 1 Kawasaki Steel Co., Ltd. Technical Research Division

Claims (2)

[Claims] 1. An apparatus comprising a conveying means for continuously transferring a semiconductor substrate, and arranging a plurality of processing chambers for subjecting the semiconductor substrate to a surface treatment along a transfer path by the conveying means, said apparatus comprising: At least one of the processing chambers on the upstream side of the transfer path is a processing chamber for performing an organic compound treatment, and the rest is thermal CVD.
An apparatus for manufacturing a semiconductor device, which is a processing chamber in which an insulating film is formed by using. 2. The semiconductor device manufacturing apparatus according to claim 1, wherein the organic compound treatment is one selected from an exposure treatment of an organic compound, a curtain flow coating treatment, and a spray coating treatment.