JPH0811178B2 - High temperature reaction processor - Google Patents

Description

TECHNICAL FIELD The present invention relates to a high-temperature reaction treatment apparatus, and more particularly to a high-temperature reaction treatment apparatus suitable for treating a radiation-sensitive resin layer with a silicon compound or an amine compound.

[Prior Art] Conventionally, in the manufacture of semiconductor devices such as ICs and LSIs, a quinonediazide compound is mixed with a negative photoresist or novolak resin in which polyisoprene or polybutadiene cyclized compound is mixed with his azide on a substrate to be processed. A photolithography method has been adopted, in which a radiation-sensitive resin such as a positive photoresist is coated, exposed by using a g-line (wavelength 436 nm) or i-line (365 nm) of a mercury lamp, and developed with a developer. .

However, in recent years, LSIs have been further miniaturized, and the minimum dimension of a circuit pattern to be formed on a substrate is entering a region of 1 μm or less. In such a dimension region, even if the conventional photolithography method is used. In particular, when a substrate having a step structure is used, there is a problem that sufficient resolution cannot be achieved due to the influence of light reflection during exposure and the problem of shallow depth of focus in the exposure system.

In order to solve such a problem, JP-A-61-107346
In the publication, similarly to the conventional photolithography method, after exposing a circuit pattern using g-line or i-line of a mercury lamp or using far-ultraviolet light, the exposed or unexposed part is exposed by, for example, a treatment with a silicon compound. A method has been proposed in which anisotropic etching is performed using reactive plasma or the like after selective silylation.

[Problems to be Solved by the Invention] An object of the present invention is to provide a high-temperature reaction treatment apparatus which can be suitably used for treatment with a silicon compound in the method proposed in the above-mentioned JP-A-61-107346. To provide.

[Means for Solving Problems] In order to achieve such an object, the high temperature reaction processing apparatus of the present invention has a hole diameter for guiding a gas of a reactive compound, which is positioned above a substrate to be processed so as to face the substrate. In the reactor, an upper heating plate having a plurality of pores of 20 μm to 2 mm on the opposite surface of the substrate, and a lower heating plate located below the substrate and directly or indirectly holding the substrate. And holding the substrate at a high temperature in a closed space formed between the upper heating plate and the lower heating plate in a vacuumable manner so that the gas of the reactive compound is introduced. It is a feature.

In the present invention, the reactor is not particularly limited as long as it can be kept in a sealed state, but it is preferable that the pressure can be reduced in order to rapidly introduce the reactive compound into the reactor.

In the present invention, it is desirable that the heating plates are arranged above and below the substrate to be processed, and that the lower heating plate is in close proximity and optimally in contact with the substrate, while the upper heating plate is The plate is preferably placed in close proximity on the substrate so that the reactive compound is uniformly introduced into the reactor.
The preferable distance between the substrate and the upper heating plate is 2 mm to 20 mm.

In the present invention, examples of materials for forming the upper and lower heating plates include aluminum, stainless steel, and Hastelloy. These heating plates are usually 50 to 250 ° C., preferably 70 to 2 at the time of processing the substrate.
It is heated to 00 ° C.

In the present invention, in order to bring the reactive compound into uniform contact with the substrate, the reactive compound is introduced into the reactor through a plurality of pores, preferably pores. The diameter of this pore is usually 20μ
It is m to 2 mm. The plurality of holes for introducing the reactive compound onto the substrate are not particularly limited as long as they are installed at positions where the reactive compound can be uniformly and quickly introduced onto the substrate, but on the surface of the upper heating plate facing the substrate. Is preferably provided in the.

Furthermore, so that the reactive compound acts uniformly on the substrate,
For example, the holes are arranged radially from the center of the upper heating plate, and the inner diameter of the holes is increased or the number of holes is increased so that the flow rate of the reactive compound increases toward the outside of the upper heating plate. Is preferred. Further, the upper heating plate may have a mesh shape.

When the reactive compound is introduced into the reactor, it is usually introduced in a gaseous state. In this case, the reactive compound gas is introduced together with an inert carrier gas such as nitrogen, argon or helium. Alternatively, it may be directly introduced into the vacuumed reactor as a liquid, for example, in the form of a mist, and gasified in the reactor. The flow rate of the gas when introducing the reactive compound in a gaseous state into the reactor is usually 0.01 to 10 l / min, and the time for contacting the gas of the reactive compound with the substrate is usually 10 seconds to
It is 5 minutes, preferably 10 seconds to 3 minutes. The concentration of the reactive compound gas in the reactor is usually 1 to 50% by volume, preferably 1 to 30% by volume. Furthermore, the total pressure in the reactor is usually 50 to 900 mmHg, preferably 200 to 760 mmHg.

Examples of the substrate to which the high-temperature reaction treatment is applied in the apparatus of the present invention described above include semiconductor substrates having a radiation-sensitive resin layer such as silicon, gallium, and arsenic, glass substrates, and diamond substrates. Here, examples of the radiation-sensitive resin include a radiation-sensitive resin composed of an alkali-soluble resin such as a novolac resin or polyhydroxystyrene and a quinonediazide compound or a bisazide compound, and particularly an alkali-soluble resin having a hydroxyl group. It is preferable to use a condensate of a quinonediazide compound or an alkali-soluble resin having an azide group in its side chain.

As the reactive compound is brought into contact with the radiation-sensitive resin layer of a substrate having a radiation-sensitive resin layer, hexamethyldisilazane, N- trimethylsilyl acetamide, N ₁ 0-
Examples thereof include silicon compounds such as bis (trimethylsilyl) acetamide, vinyltrichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane.

According to the present invention, a substrate having a radiation-sensitive resin layer irradiated with radiation such as light in a pattern is placed on a heated lower heating plate, and the heated upper heating plate is placed on the substrate. To carry out the reaction treatment of silylation in a high temperature reaction gas atmosphere in a short time by supplying silicon compounds that are reactive compounds from a plurality of pores with a pore size of 20 μm to 2 mm while keeping them close to each other. You can

Hereinafter, embodiments of the present invention will be described in detail and specifically with reference to the drawings.

FIG. 1 shows an embodiment of the present invention. Here, 1A and 1B are an upper member and a lower member of the reactor 1 which can be separated into upper and lower parts, and the reactor 1 can be kept in a sealed state by moving the lower member 1B upward. Although the upper member is fixed here, the lower member may be fixed. 2 is an upper heating plate, 3 is a lower heating plate, 4
Is a seal member that is provided on the reactor lower member 1B side and is kept at a high temperature by being connected to the lower heating plate 3, and is used for upper heating when the reaction chamber 1 is closed by the upper member 1A. The space between the plate 2 can be kept airtight.

Reference numeral 5 denotes a substrate placed on the lower heating plate 3 and subjected to a high temperature reaction treatment. The substrate 5 has a radiation-sensitive resin layer subjected to a radiation irradiation treatment, and keeps the reactor 1 in a sealed state. At this time, an appropriate gap is maintained between the substrate 5 and the upper heating plate 2 as described above. The upper heating plate 2 has a large number of pores 6 on its surface facing the substrate 5 as shown in FIG. 2, and the reactivity of the silicon compound stored in the bubbler 7 is increased. The compound gas can be fed through this pore 6 together with an inert carrier gas if desired. Here, as shown in FIG. 3, the upper heating plate has a mesh shape with a pore diameter of about 20 μm to 2 mm, and may serve as the heating plate and the pores for introducing the reactive compound. In addition, the bubbler 7 is provided with a hot water supply system 8, and by controlling the temperature of the bubbler 7 with the hot water and adjusting the temperature of the silicon compound, the reaction sent together with the inert carrier gas in the reactor 1 In addition to adjusting the concentration of the reactive compound gas, the flow rate of the inert carrier gas can be controlled by a flow rate control device such as a mass flow controller (not shown) to appropriately control the supply amount of the reactive compound. Reference numeral 9 is a heating device for avoiding the condensation of the reactive compound gas.

Further, 10 is a decompression pump, 11 is a condenser, 12 is a trap for the reactive compound gas, and when the treatment is completed, the gas containing the high temperature reactive compound gas is cooled by the condenser 11 and the condensed reaction The volatile compound can be introduced into the trap 12 by the pump 10.

In the high temperature reaction processing apparatus configured as described above, the substrate 5 after the latent image of the circuit pattern is formed by the radiation irradiation processing is placed on the lower heating plate 3 of the reactor 1, and the reactor lower member 1B is placed. By raising the temperature, the reactor 1 is closed. In this case, the upper heating plate 2 and the lower heating plate 3 are maintained at 50 ° C to 250 ° C, and the substrate 5
The periphery of is sealed airtight between the seal member 4 and the upper heating plate 2.

Therefore, the vacuum degree 10 is applied to the periphery of the substrate 5 so that
The pressure is reduced to about 500 mmHg, and then the reactive compound gas is discharged from the bubbler 7 to the substrate 5 through the pores 6 of the upper heating plate 2 using nitrogen as an inert carrier gas. The concentration of the reactive compound gas at this time is controlled by the above-mentioned method, and thus the substrate 5 is usually in the atmosphere of the reactive compound gas for 10 seconds to 5 minutes, preferably
It is left for 10 seconds to 3 minutes.

Further, in this case, the periphery of the substrate 5 may be controlled so that the reactive compound gas may flow constantly or intermittently. Then, when the reaction is completed, the high temperature reactive compound gas is guided to the condenser 11 by the pump 10, cooled, and then trapped.
Recovered to 12.

In the present embodiment, the heating plates 2 and 3 are arranged in the reactor 1. However, in order to further improve the productivity, the pressure may be reduced or reduced so that the substrate 5 is heated before being brought into the reactant 1. A means for heating in an atmosphere of normal pressure may be provided.

[Example] A partial esterified product of 6-diazo-5.6-dihydro-5-oxo-1-naphthalenesulfonic acid chloride and a novolac resin was applied onto a silicon wafer by spin coating, and the g-line having an opening coefficient of 0.42. It was exposed using a stepper. Next, the silicon wafer was placed in the above reactor having a stainless steel upper heating plate having a plurality of 50 μm pores and a stainless steel lower heating plate, and hexamethyldisilazane (HMDS) (HMDS bubbler temperature 50 ° C. , N ₂ flow rate 10 l / min) was introduced into the reactor, then sealed and the total pressure was 760 m.
Silylation was performed at 140 ° C. for 1 minute with mHg and HMDS concentration of 6.6% by volume.

When this wafer was oxygen-etched using MRC magnetron reactive ion etching equipment MIE760, 0.6 μm equally spaced line-and-space patterns were formed on an aluminum substrate with 0.7 μm steps as designed. I knew that.

EFFECTS OF THE INVENTION As described above, according to the high temperature reaction processing apparatus of the present invention, the high temperature reaction processing device is located above the substrate to be processed,
An upper heating plate having a plurality of pores for guiding a gas of a reactive compound on the opposite surface of the substrate, and a lower heating plate positioned below the substrate and directly or indirectly holding the substrate. Hold the substrate at a high temperature in a closed space that is provided in the reactor and is formed between the upper heating plate and the lower heating plate in a vacuumable manner so that the gas of the reactive compound is introduced. Therefore, for example, by supplying a reactive compound gas composed of a silicon compound, the radiation-sensitive radiation-sensitive resin layer is subjected to a reaction treatment, and then a dry development treatment is performed to perform ultrafine processing with a resolution of 1.0 μm or less. It has become possible to carry out with high precision in a short time while maintaining high productivity.

Further, by supplying a gas of a reactive compound consisting of an amine compound and subjecting the radiation-sensitive resin layer subjected to radiation irradiation to a reaction treatment and developing with a strong alkaline aqueous solution, an image reversal process capable of carrying out fine processing can be performed. Can also be preferably used.

Furthermore, the present invention provides an amine compound treatment in an image reversal process capable of performing fine processing by subjecting a substrate having a radiation-sensitive resin layer subjected to radiation irradiation treatment to an amine compound treatment and developing with a strong alkaline aqueous solution. Can also be preferably used. Here, examples of the amine compound include ammonia, trimethylamine, triethylamine, and the like.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an example of the configuration of the high temperature reaction treatment apparatus of the present invention in a sealed state, FIG. 2 is a bottom view of the upper heating plate, and FIGS. 3 (A) and 3 (B) are for upper heating. It is a bottom view and a side view showing another example of a board. 1 ... Reactor, 1A ... Upper member, 1B ... Lower member, 2 ...
... Upper heating plate, 3 ... Lower heating plate, 4 ... Seal member, 5 ... Substrate, 6 ... Pore, 7 ... Bubler, 10 ...
Decompression pump, 11 …… condenser, 12 …… trap.

Claims (1)

[Claims] 1. A pore size for introducing a gas of a reactive compound is 20 μm to 2 m, which is located above a substrate to be processed so as to face it.
An upper heating plate having a plurality of pores of m on the opposite surface of the substrate, and a lower heating plate located below the substrate and directly or indirectly holding the substrate were provided in the reactor. The substrate is kept at a high temperature in a closed space that can be vacuumed between the upper heating plate and the lower heating plate, and the gas of the reactive compound is introduced. High temperature reaction processing equipment.