JP2002293629A - Electroconductive ceramic material, component for electrode, electrostatic polarizer, and charged particle beam exposing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electroconductive ceramic material which has a specific electrical resistance of about 10<-1> Ωcm at room temperature and whose specific electrical resistance is lowered, and the surface is stable even when the ceramic material is subjected to oxygen plasma treatment. SOLUTION: The electroconductive ceramic material is formed from oxide particles selected from RuO2 , ReO2 , IrO2 and a specific fixed perovskite oxide group and auxiliary particles selected from LiF, Li3 PO4 , Li2 CO3 , Li2 SO4 , Bi2 O3 , Bi-compound oxides, PbO and Pb-compound oxides.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a conductive ceramic material and its use. More specifically, the present invention relates to a conductive ceramic material, an electrode component formed from such a ceramic material, an electrostatic deflector constituted by such an electrode component, and a charged particle beam provided with such an electrostatic deflector. The present invention relates to an exposure apparatus. INDUSTRIAL APPLICABILITY The present invention can be advantageously used for manufacturing semiconductor devices and other devices.

[0002]

2. Description of the Related Art As is well known, in a device such as a DRAM (Dynamic Random Access Memory), the degree of integration is increasing year by year, and a DRAM having a storage capacity of 1 gigabit (1 Gbit) has recently appeared. are doing. It is considered that a charged beam exposure technique is indispensable for manufacturing the 1 Gbit or 4 Gbit DRAM. To date, as interconnect dimensions have shrunk, the light source for lithography has changed from the g-line and i-line
F and ArF lasers have shifted to shorter wavelengths. However, in the case of an electron beam (EB) exposure technique using a charged beam having a shorter wavelength, typically an electron beam as a light source, an electron beam (EB) exposure technique of 0.05 μm or less is used. 0.02μm fine pattern
This is because it can be easily formed with the following alignment accuracy.

As described in detail below with reference to FIG. 1, an EB exposure apparatus uses LaB ₆ or the like as a beam source, and converts thermoelectrons generated from the beam source into various filters,
After changing the position, shape, and the like of the electrons with a mask and a deflector, a pattern is directly drawn on a resist film formed on the surface of the substrate to be processed. In order to change the position of electrons, two types of deflection methods are used, deflection by a magnetic field and deflection by an electric field. The magnetic field deflection is used in the main deflection area in units of millimeters.
Used in the sub-deflection area within 00 microns.

In a conventional EB exposure apparatus, since a resist film is formed on a substrate to be processed, it is inevitable that a part of the resist film is scattered with the EB exposure.
As a result, during the repetition of the exposure operation, on the deflection electrodes constituting the electrostatic deflector arranged in the EB exposure apparatus,
It is inevitable that an organic film resulting from the scattered resist film is formed. The organic film on the deflection electrode is generally an insulating film, and tends to cause charge-up.

Therefore, in a conventional EB exposure apparatus, after a predetermined operation time has elapsed, oxygen plasma is generated in a lens barrel provided therein to remove an organic insulating film deposited on a deflection electrode. Is being done. However, in the EB exposure apparatus, since the electrostatic deflector is used in the magnetic field formed by the electromagnetic lens or the electromagnetic deflector, the deflection electrode of the electrostatic deflector is made of a metal having a low specific resistance (specific electric resistance). When formed by, eddy current is generated in the deflection electrode,
There is a problem that the magnetic field formed by such an eddy current shifts the position of the electron beam deflected by the electrostatic deflector. For this reason, the deflection electrode of the electrostatic deflector preferably has a specific electric resistance of about 1 × 10 ⁻¹ Ω · cm at room temperature, and is generally made of a conductive ceramic material such as Al ₂ O ₃ , TiC or the like. It is composed of a composite material in which a thin metal film of Au, Pt or the like is adhered on a substrate made of a material.

However, when a conductive ceramic material such as Al ₂ O ₃ or TiC is used as a deflection electrode of an electrostatic deflector, if the above-described cleaning process using oxygen plasma is performed, the material is included in the deflection electrode. Ti is oxidized, and as a result, the specific electric resistance of the deflection electrode changes. In a deflection electrode having a structure in which a base made of a ceramic material is covered with a metal film, the metal film is etched by being subjected to sputtering, and as a result, the specific resistance value of the deflection electrode also changes. Therefore, it is necessary that the deflection electrode is made of a material that can withstand oxygen plasma processing, that the specific resistance value does not change even after oxygen plasma processing, and that the surface is not oxidized or etched.

Furthermore, Japanese Patent Application Laid-Open No. 9-293472 discloses an example in which a carbon material is used as a deflection electrode of an electrostatic deflector. By using a carbon material as the deflection electrode, the problem of consumption of the metal film can be solved even when the cleaning process is performed in oxygen plasma. However, in such a conventional configuration, the carbon electrode itself is consumed by the treatment in the oxygen plasma.

For the reasons described above, in the conventional EB exposure apparatus, it is necessary to frequently replace the electrostatic deflector used. The EB exposure apparatus not only has such a short service life, but also the replacement of the electrostatic deflector involves a troublesome adjustment process such as alignment of the electron optical system. As a result, the EB exposure apparatus is used. In the manufacturing process of a semiconductor device, a substantial decrease in throughput cannot be avoided.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a 1 × 1 at room temperature.
A conductive ceramic material having a specific electrical resistance of about 0 ^-1 Ω · cm, whose specific resistance is not reduced by the oxygen plasma treatment, and whose surface is not adversely affected by the oxygen plasma treatment. To provide.

Another object of the present invention is to provide a conductive ceramic material capable of simultaneously improving the throughput and extending the life of the apparatus when used as an electrode material in a charged particle beam exposure apparatus. Further, an object of the present invention is to have a specific electric resistance value of about 1 × 10 ⁻¹ Ω · cm at room temperature, to prevent the specific resistance value from being lowered by the oxygen plasma treatment, and to have the surface thereof treated with the oxygen plasma. An object of the present invention is to provide an electrode component which is not adversely affected by the above.

Another object of the present invention is to not only move the spot position of a beam accurately and quickly when mounted on a charged particle beam exposure apparatus, but also to improve throughput and extend the life of the apparatus. It is to provide an electrostatic deflector which can be achieved at the same time. Still further, an object of the present invention is to be able to be advantageously used for forming a fine resist pattern in the manufacture of a highly integrated semiconductor device or the like, to improve the throughput and to use an electrostatic deflector for a long time. An object of the present invention is to provide a charged particle beam exposure apparatus that does not require replacement.

The above and other objects of the present invention can be easily understood from the following detailed description.

[0013]

SUMMARY OF THE INVENTION The present invention provides one aspect thereof.
, A conductive cell mainly composed of oxide ceramics
Lamix material, ruthenium oxide (RuO
_Two ), Rhenium oxide (ReO_Two ), Iridium oxide (I
rO_Two ), And various perovskite oxides, SrV
O_Three , CaVO_Three , LaTiO_Three , SrMoO_Three , Ca
MoO_Three , SrCrO_Three , CaCrO_Three , LaVO_Three ,
GdVO_Three , SrMnO_Three , CaMnO_Three , NiCrO
_Three , BiCrO _Three , LaCrO_Three , LnCrO_Three , Sr
RuO_Three , CaRuO_Three , SrFeO_Three, BaRuO
_Three , LaMnO_Three , LnMnO_Three , LaFeO_Three , Ln
FeO_Three , LaCoO_Three , LaRhO_Three , LaNiO
_Three , PbRuO_Three , Bi_Two Ru_Two O₇, LaTaO_Three ,
SrRuO_Three , PbRuO_Three And BiRuO_ThreeConsists of
At least one oxide particle selected from the group;
F, Li_Three PO_Four , Li_Two CO_Three , Li_Two SO_Four , Bi
_Two O_Three , Bi-containing composite oxides, including PbO and Pb
At least one selected from the group consisting of composite oxides
Characterized by being formed from auxiliary particles
In conductive ceramic materials.

According to another aspect of the present invention, there is provided a semiconductor device formed of at least one kind of metal particles having resistance to oxidation and at least one kind of inorganic glass particles. Characteristic conductive ceramic material. Further, in another aspect, the present invention resides in an electrode component comprising the conductive ceramic material of the present invention.

Still further, according to the present invention, there is provided, in another aspect thereof, a deflection electrode formed of the conductive ceramic material of the present invention. In the deflector. Still further, in another aspect, the invention is adapted to carry a vacuum chamber, a charged particle beam source disposed in the vacuum chamber, and a substrate disposed in the vacuum chamber, the substrate being processed. A stage member, an electromagnetic lens arranged between the charged particle beam source and the stage member in the vacuum chamber, and an electromagnetic lens arranged between the charged particle beam source and the stage member in the vacuum chamber. A charged particle beam exposure apparatus provided with an electrostatic deflector provided, wherein the electrostatic deflector comprises a deflection electrode made of the conductive ceramic material of the present invention. In the exposure equipment.

The conductive ceramic material of the present invention is stable against oxygen plasma treatment. Therefore, even when oxygen plasma is generated in the lens barrel for cleaning in a charged particle beam exposure apparatus, the conductive ceramic material is deflected. The specific electrical resistance of the electrode does not change. Also, for example, the specific electric resistance of the deflecting electrode can be reduced to about 1 × 10 ⁻¹ Ω · cm by which the eddy current can be effectively suppressed by appropriately setting the mixing ratio of the starting materials of the conductive ceramic material. Can be set.

Further, by manufacturing a deflection electrode using the ceramic material of the present invention, the deflection electrode is formed in a magnetic field (40 Gauss).
In (in), a positional accuracy of 0.01 μm or less can be obtained in a short time within 50 μsec. In other words, in the charged particle beam exposure apparatus equipped with the deflection electrode according to the present invention, the beam settling time can be suppressed within 50 μsec. Further, in the charged particle beam exposure apparatus of the present invention, 3 μA / 5
When a substrate to be processed is irradiated with a charged particle beam of 0 KV, 1
The drift amount after 0 seconds can be reduced to 10 nm or less,
Further, when the substrate is irradiated with 30 W, 1 Torr oxygen plasma for 20 seconds, the drift amount can be reduced to 10 nm or less again.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Conductive ceramics according to the present invention
The material is a composite composition of the first component and the second component.
It can be roughly divided into the following two forms
it can. The first conductive ceramic material is as follows:
It is a composite composition of the components. Ru particles of at least one kind of oxide (first component)
O_Two , ReO_Two , IrO_Two , SrVO_Three , CaVO_Three ,
LaTiO_Three , SrMoO_Three , CaMoO_Three , SrCr
O_Three , CaCrO_Three , LaVO_Three , GdVO_Three , SrM
nO_Three , CaMnO_Three , NiCrO_Three , BiCrO_Three ,
LaCrO _Three , LnCrO_Three , SrRuO_Three , CaRu
O_Three , SrFeO_Three , BaRuO_Three, LaMnO_Three , L
nMnO_Three , LaFeO_Three , LnFeO_Three , LaCoO
_Three , LaRhO_Three , LaNiO_Three , PbRuO_Three , Bi
_Two Ru_Two O₇ , LaTaO_Three, SrRuO_Three , PbRu
O_Three , BiRuO_Three. Particles of at least one auxiliary agent (second component) Li
F, Li_Three PO_Four , Li_Two CO_Three , Li_Two SO_Four , Bi
_Two O_Three Oxide containing Pb, Bi, complex oxide containing PbO, Pb
Oxide.

In the first conductive ceramic material,
In a matrix composed of oxide particles such as RuO ₂ , Li
Particles of an auxiliary agent such as F are dispersed. An auxiliary agent such as LiF can function as an auxiliary agent for sintering the oxide particles. The term "particle", when used herein, is used in a broad sense and encompasses various particles that can be used in the practice of the present invention, i.e., powders, fine particles, coarse particles, and the like. ing. Generally, oxide particles such as RuO ₂ have an average particle size of about 0.05-0.3 μm, preferably about 0.08-0.2 μm. I have. The particles of the sintering aid such as LiF used in combination with the oxide particles are usually about 1.0 to
It has an average particle size of 5.0 μm, and preferably has an average particle size of about 2.0-4.0 μm.

The first conductive ceramic material preferably has a coefficient of thermal expansion of 10 ⁻⁵ / ° C. or less. This is because when a component having a complicated shape is manufactured from this ceramic material or when a complicated assembly process is involved, the occurrence of defects such as displacement and cracks due to thermal expansion can be effectively prevented. Further, the first conductive ceramic material is preferably 1 × 1 at room temperature (about 25 ° C.).
Specific electric resistance (specific resistance) in the range of 0 ^-4 to 1 × 10 ⁴ Ω · cm, more preferably 1 × 10 ^-2 to 1 × 10 ² Ω · cm.
It has a specific electrical resistance of cm. Therefore, when a deflection electrode of an electrostatic deflector is manufactured using such a ceramic material, it is possible to prevent a problem of a displacement of an electron beam due to generation of an eddy current.

Further, according to the present invention, setting the specific electric resistance value within the above-mentioned preferred range is based on the mixing ratio of the oxide particles such as RuO ₂ used as the starting material and the auxiliary particles such as LiF. Can be easily and accurately performed by appropriately adjusting. Generally, RuO ₂
Since the specific electric resistance value decreases as the blending ratio of the oxide particles such as RuO ₂ increases, the ratio of the oxide particles such as RuO _{2 is} about 15 to 70 based on the total amount (volume) of the conductive ceramic material. %, More preferably in the range of about 20-30%.

The second conductive ceramic material is composed of at least one kind of metal particles (first component) having resistance to oxidation and at least one kind of inorganic glass particles (second component). It is a composite composition. In this composite composition, the metal used as the first component is preferably Au, Pt or a combination thereof. Au
Examples of the combination of Pt and Pt include alloys or mixtures of these metals or compounds thereof. Further, the inorganic glass used as the second component is preferably an inorganic glass having a softening point of 400 ° C. or higher. It is preferable that such an inorganic glass further has a composition substantially free of a volatile metal element such as lead. This is because lead and the like receive a reducing action while being used in a vacuum atmosphere and exhibit conductivity. Inorganic glasses useful in the practice of the present invention include, but are not limited to, those listed below, borosilicate glasses,
Aluminosilicate glass etc. can be mentioned.

In the second conductive ceramic material, metal particles such as Au and Pt are dispersed in a matrix made of inorganic glass. Here, the inorganic glass particles have an average particle size of about 1.0 to 5.0 μm,
Preferably, it has an average particle size of about 2.0-4.0 μm. The metal particles used in combination with the inorganic glass particles usually have an average particle size of about 0.1 to 20 μm, preferably about 0.1 to 5 μm. are doing.

Like the first conductive ceramic material,
The second conductive ceramic material is also preferably 10 ^-5.
/ ° C or less. This is because when a component having a complicated shape is manufactured from this ceramic material or when a complicated assembly process is involved, the occurrence of defects such as displacement and cracks due to thermal expansion can be effectively prevented.

Similarly, the second conductive ceramic material is preferably 1 × 1 as measured at room temperature (about 25 ° C.).
It has a specific electric resistance value in the range of 0 ^-4 to 1 × 10 ⁴ Ω · cm, more preferably a specific electric resistance value of 1 × 10 ⁻² to 1 × 10 ² Ω · cm. Therefore, when a deflection electrode of an electrostatic deflector is manufactured using such a ceramic material, it is possible to prevent a problem of a displacement of an electron beam due to generation of an eddy current.

Further, setting the specific electric resistance value in the preferable range as described above means that according to the present invention, by appropriately adjusting the mixing ratio of the inorganic glass particles and the metal particles used as starting materials, It can be done easily and accurately. In general, the specific electrical resistance value decreases as the mixing ratio of the inorganic glass increases, so that the ratio of the inorganic glass particles is in the range of about 10 to 80% based on the total amount (volume) of the conductive ceramic material. And more preferably in the range of about 40-80%.

Although the conductive ceramic material of the present invention can have various forms depending on needs, it is generally preferable to have a form of a fired molded body. Such shaped bodies can be manufactured according to various techniques as desired, and thus can have various shapes and dimensions. In the following, some preferred production methods are described.

For example, a fired molded body can be produced by molding and firing raw material particles, and then machining the obtained bulk body. This manufacturing method preferably comprises
For example, a step of mixing raw material particles having a predetermined particle size at a predetermined compounding ratio, a step of forming the precursor by compacting the obtained mixture by compaction molding or another molding method, a step of forming a precursor obtained, A step of firing the body to form a fired body (also referred to as a “bulk body” in the present invention), and machining the bulk body to finally form a desired shape such as a deflection electrode of an electrostatic deflector. It can be performed by a process.

In this production method, the step of mixing the raw material particles can be performed using a conventional mixing apparatus, for example, a ball mill. The subsequent molding step can also be performed using a conventional molding machine and molding conditions. The precursor firing step can be performed by placing the precursor in a suitable firing furnace and then heating the precursor at a high temperature of, for example, about 900 to 1000 ° C. for about 60 to 300 minutes. The last machining step can be performed, for example, using a lathe, milling machine, or other cutting device. If necessary, the obtained product may be finished by polishing or the like.

According to another method, the fired molded body is formed by molding raw material particles to obtain a molded body having a predetermined shape, and then firing the obtained molded body and, if necessary, finishing. It can also be manufactured by More specifically, the production method includes, for example, a step of mixing raw material particles having a predetermined particle size at a predetermined compounding ratio, molding the obtained mixture by injection molding or other molding methods, A step of finally forming a molded article substantially equivalent to a desired shape such as a deflection electrode of an electric deflector, a step of firing the obtained molded article to form a fired molded article, and a step of finishing the fired molded article Can be implemented.

As in the above-described production method, in this production method, the mixing step of the raw material particles and the subsequent molding step and firing step can be advantageously performed using ordinary equipment and processing conditions. The final finishing step can be performed using, for example, an abrasive, alumina particles, diamond particles, or the like. In another preferred embodiment, the conductive ceramic material of the present invention can have a form of a coating. Such a ceramic material can more preferably have the form of a coating applied to the surface of a metal workpiece. Here, the metal processed body serving as a base of the coating is not particularly limited, and examples thereof include an arbitrary metal product given a predetermined shape by a processing method such as machining, casting, or injection molding. it can. Examples of suitable metals include stainless steel, aluminum, copper, and the like. In some cases,
A processed body other than metal may be used as a base.

Generally, a coating made of a conductive ceramic material can be formed by obtaining a metal workpiece having a predetermined shape and then applying a coating made of raw material particles on the surface of the metal workpiece. Suitable coating methods include spin coating, dip coating and other coating methods,
Examples thereof include a vacuum deposition method, a sputtering method, a chemical vapor deposition method, a plasma spraying method, electroplating, and electroless plating. The thickness of such a coating can be varied in a wide range depending on the use of the coating, but is usually in the range of about 1 to 500 μm, preferably in the range of about 10 to 200 μm.

The conductive ceramic material of the present invention can be advantageously used in various fields because of its excellent properties, and can be particularly advantageously used as an electrode material or as an electrode component. The effect of the electrode component of the present invention is particularly remarkable when it is used in a magnetic field. Therefore, the electrode component of the present invention can be used particularly advantageously as an electrostatic deflector used in a charged particle beam exposure apparatus. Further, the conductive ceramic material of the present invention can be advantageously used also as a stage member used for supporting a substrate to be processed in a charged particle beam exposure apparatus, and other members.

According to the present invention, there is further provided a charged particle beam exposure apparatus. A charged particle beam exposure apparatus according to the present invention includes a vacuum chamber, a charged particle beam source provided in the vacuum chamber, a stage member provided in the vacuum chamber and adapted to carry a substrate to be processed, and a vacuum. In the room, an electromagnetic lens disposed between the charged particle beam source and the stage member, and, in a vacuum chamber, including an electrostatic deflector disposed between the charged particle beam source and the stage member, The electrostatic deflector comprises a deflection electrode composed of the conductive ceramic material of the present invention.

In another aspect, in the charged particle beam exposure apparatus of the present invention, the stage member may be further made of the conductive ceramic material of the present invention. In still another aspect, a charged particle beam exposure apparatus of the present invention comprises:
The inner wall of the vacuum chamber may further include a liner made of the conductive ceramic material of the present invention.

Subsequently, a charged particle beam exposure apparatus of the present invention will be described with reference to the accompanying drawings. FIG. 1 is a schematic diagram schematically showing a preferred embodiment of the charged particle beam exposure apparatus of the present invention. Referring to FIG. 1, a charged particle beam exposure apparatus 10 includes a beam source 11 such as an electron gun made of LaB ₆ or the like in a lens barrel 10A. In the optical path of a charged particle beam such as electrons emitted from the electron gun 11 along a predetermined optical axis and reaching the substrate 13 held on the movable stage 12, electromagnetic lenses 14A to 14F are provided on the upstream side. And are arranged in order from the downstream side.

In the charged particle beam exposure apparatus 10, the charged particle beam emitted from the beam source 11 is first shaped into a rectangular shape by passing through a beam shaping plate 15 having a rectangular aperture. Electromagnetic lens 1
4A and 14B focus on the block mask 16 in which a number of fine beam shaping apertures are formed in the form of a parallel beam. An electromagnetic deflector 16A and an electrostatic deflector 16B are provided near the block mask 16,
By driving them, the rectangular charged particle beam is deflected from a predetermined optical axis, and is shaped into a desired selected shape by passing through a selected aperture in the block mask 16.

The charged particle beam shaped into the shape selected as described above is further applied to the electromagnetic lens 14C.
Is returned to a predetermined optical axis, and is reduced by the electromagnetic lenses 14D and 14E constituting the reduction optical system, and then focused on the substrate 13 on the stage 12 by the electromagnetic lens 14F. That is, the electromagnetic lens 14F functions as an objective lens.

Further, an electromagnetic lens 1 is provided in the lens barrel 10A.
An electrostatic deflector 20 and an electromagnetic deflector 18 for deflecting the charged particle beam focused on the substrate 13 to scan on the surface of the substrate 13 are provided near 4F. Among them, the electromagnetic deflector 18 includes a coil, and scans the charged particle beam at a relatively low speed over a wide area of about several millimeters square on the surface of the substrate 13 by the generated magnetic field. The device 20 is composed of an electrode plate, and generates a charged particle beam by the generated electric field.
3. A very high-speed scan is performed in a limited area of about 100 μm square on the surface of No. 3. Similarly, the electromagnetic deflector 16A
Causes the charged particle beam to scan a wide area on the block mask 16 at a low speed by the generated magnetic field, whereas the electrostatic deflector 16B causes a limited area on the block mask 16 to be scanned by the generated electric field. Scan very fast.

In the charged particle beam exposure apparatus 10 shown in FIG.
Further, another electrostatic deflector 19 is provided in the lens barrel 10A, and by driving this, the charged particle beam on the substrate 13 is turned on and off at high speed. As a result, the substrate 13 on the stage 12 is turned off. Is exposed at a high speed by a charged particle beam having a desired shape. Further, below the stage 12, an immersion lens 11B used for optical axis alignment of the charged particle beam is formed.

FIGS. 2 and 3 show the electrostatic deflector 2 respectively.
0 is a perspective view and a cross-sectional view showing the configuration of FIG. FIG. 3 shows FIG.
FIG. 3 is a sectional view taken along line III-III of FIG. 2 and 3
The electrostatic deflector 20 includes a cylindrical member 21 formed of an insulator such as Al ₂ O ₃ and a cylindrical member 21 formed on an inner wall surface of the cylindrical member 21 in parallel with each other via a separation groove 23. A plurality of electrode members 22 are provided, and a charged particle beam such as an electron beam passes through a substantially cylindrical path defined by the plurality of electrode members 22 through a predetermined optical axis (in the figure, (Indicated by EB). At this time, the charged particle beam is deflected from the optical axis EB by applying a drive voltage to a selected portion of the plurality of electrode members 22.

As can be seen from the sectional view of FIG. 3, each electrode member 22 is electrically and spatially separated from the inner wall surface of the cylindrical member 21 on the inner wall surface of the cylindrical member 21. Are formed so as to interlock with each other so as to continuously cover when viewed from the optical axis EB. For this reason, the inner wall surface of the insulating cylindrical member 21 is exposed, and the problem of charging up by the charged particle beam is avoided. The electrode member 22 is formed on the inner wall surface 21 of the cylindrical member 21.
A is fixed on A by an adhesive.

FIG. 4 shows the electrode member 2 shown in FIG. 2 and FIG.
2 shows a state in which one of them is taken out of the electrostatic deflector 20. Referring to FIG. 4, the electrode member 22 has a relatively complicated shape. However, according to the present invention, the electrode member 22 can be manufactured easily and with a high yield by using the above-described method. At this time, by appropriately adjusting the mixing ratio of the raw material particles, a specific electric resistance value of about 1 × 10 ⁻¹ Ω · cm that can effectively prevent generation of eddy current can be realized. Further, since the electrode member 22 thus formed is made of a composite ceramic material having a specific composition according to the present invention, when the electrode member 22 is used as the electrostatic deflector 20 in the charged particle exposure apparatus 10 of FIG.
Even if cleaning is repeatedly performed in oxygen plasma, the electrical characteristics do not deteriorate.

Although the exact reason has not been clarified yet, it is considered that the prevention of the deterioration of the electric characteristics as described above largely depends on the characteristics of the oxide particles used as the raw material particles. For example, referring to a Ru—O-based oxide, its phase equilibrium diagram is not completely determined at this time. However, at low temperatures, even if the oxygen partial pressure PO ₂ is low, RuO _{2 is} higher than Ru in the metal phase. The tendency to be stable is undoubtedly confirmed. In particular, 10 ^-3 to 10 ^-2 Torr used for plasma cleaning processing in a charged particle exposure apparatus
r, ie, in the pressure range of about 0.1 to 1 Pa, 900
Considering that RuO ₂ is stable up to a temperature of about 1000 ° C. and the temperature actually used in the plasma cleaning process is much lower than this, a ceramic material containing such RuO ₂ as nonmagnetic conductive particles is considered. It is understood that the electrode member 22 is not deteriorated even if the plasma cleaning process is repeated.

In the Ru—O system, RuO ₂ +
An oxidation reaction of 1 / 2O ₂ → RuO ₃ is considered, but Ru
O ₃ is a gas at a temperature higher than room temperature, and it has been confirmed that the Gibbs free energy of the oxidation reaction is positive at least at a temperature higher than room temperature. Therefore, RuO ₂ is further oxidized in an oxidizing plasma atmosphere and gaseous RuO 2
It is unlikely that it will be removed as ₃ .

FIG. 5 is a flow sheet sequentially showing an example of a method of manufacturing the electrode member 22 of FIG. First,
In step S1, nonmagnetic conductive oxide particles typically made of RuO ₂ and sintering aid particles are mixed. If necessary, a binder resin may be used in combination. In step S2, the obtained mixture is compacted into a predetermined shape, for example, a plate-like shape.

Next, in step S3, the obtained plate-like molded body is heat-treated at a temperature of about 1000 ° C. for several hours to obtain a plate-like fired molded body in which a sintering aid is dispersed in nonmagnetic conductive oxide particles. To form Further, in step S4, step S3
Is machined. The electrode member 22 of FIG. 4 is obtained.

By the way, in the manufacturing process of FIG. 5 described above, the compact obtained in the step S2 is limited to a simple plate-shaped or column-shaped one.
Is similarly limited to those having a simple shape. For this reason, in the manufacturing process of FIG. 5, in the step S4, it is necessary to machine the obtained fired molded body to finally shape it into a desired shape.

According to another method, the above problem can be easily solved. That is, the electrode member 22 shown in FIG.
Also, the electrode member having another shape can be advantageously manufactured by the manufacturing steps shown in FIG. FIG.
In step S11, in the step S11, similarly to the step S1, after mixing particles of a nonmagnetic conductive oxide such as RuO ₂ with the particles of the sintering aid and optionally the binder resin, in the subsequent step S12, The mixture of the obtained raw material particles is supplied to an injection molding machine, and a molded body (a precursor of an electrode) having substantially the same shape and dimensions as the electrode member 22 in FIG. 4 is formed.

Next, the obtained precursor of the electrode is heated at a predetermined temperature to disperse the binder resin by thermal decomposition, and then fired in step S13. Electrode member 2 of FIG.
2 is obtained. The electrode member 22 may be subjected to finishing in step S14 as needed. In this manufacturing process, it may be necessary to perform machining in step S14, but machining in this case is simple, and as a result, the production efficiency of the electrode member 22 can be greatly increased. .

FIG. 7 shows another embodiment of the charged particle beam exposure apparatus of the present invention, and FIG. 8 shows a stage 3 used in the charged particle beam exposure apparatus 30 of FIG.
FIG. 2 is a cross-sectional view schematically showing the configuration of FIG. FIG.
The same reference numerals are given to the parts described above, and the description is omitted. Referring to FIG. 7, in the charged particle beam exposure apparatus 30, not only the electrostatic deflector 20 but also all the electrostatic deflectors, that is, the electrostatic deflectors corresponding to the electrostatic deflector 16 </ b> B and the electrostatic deflector 19. The deflection electrodes 36B and 39 are formed from the conductive ceramic material according to the present invention. As shown in FIG. 8, the stage 31 for supporting the substrate to be processed is composed of a metal base 31A and a coating 31B made of the conductive ceramic composite material of the present invention, which is applied to the surface of the base 31A. ing. By employing such a composite structure, drift of an electron beam due to eddy current generated in a conventional stage is suppressed, and high-speed and high-precision exposure can be performed.

The coating 31B shown in FIG. 8 can be easily formed by depositing the raw material powder of the composite material on the base 31A by plasma spraying. FIG.
1 shows another embodiment of the charged particle beam exposure apparatus of the present invention. In FIG. 9, the same reference numerals are given to the parts described above, and the description will be omitted.

Referring to FIG. 9, the charged particle beam exposure apparatus 40 has the same configuration as the charged particle beam exposure apparatus 30 shown in FIG. The difference is that a liner 10B made of the conductive ceramic material of the present invention is formed. By forming the liner 10B as shown from the composite ceramic material of the present invention, the electromagnetic deflector 16A and the electromagnetic lens 14A are formed.
A to 14F, or an eddy current flowing through the lens barrel 10A due to the magnetic field formed by the electromagnetic deflector 18 can be suppressed. Accordingly, the secondary magnetic field due to the eddy current is also suppressed, and the accuracy of the electron beam exposure can be improved.

The liner 10B can be easily formed by performing plasma spraying of raw material powder on the inner wall surface of the lens barrel 10A.

[0055]

The following examples serve to further illustrate the invention. Example 1 RuO ₂ powder having an average particle diameter of 1 μm
20% by volume with respect to the LiF powder of
To this, acetone and PVB (polyvinyl butyral) resin powder were added at a ratio of 2% by volume. The resulting mixture was milled in a ball mill for 20 hours.

Next, the slurry obtained by the above-mentioned milling step was dried to completely remove acetone, and then pulverized with a grinder. A raw material powder for molding was obtained. Further, the obtained raw material powder was charged into a mold and pressed into a plate at a pressure of 5 MPa. The obtained plate-like molded body was 1000
After firing in air at about 2 ° C. for about 2 hours, the fired molded body was machined. The electrode member 22 described above with reference to FIG. 4 was obtained.

The obtained electrode member 22 is approximately 1 ×, which is suitable as an electrostatic deflector used in a charged particle beam exposure apparatus.
It showed a specific electric resistance of 10 ^-1 to 1 × 10 ^-2 Ωcm.
Further, since this electrode member was entirely made of oxide, the charged particle beam exposure apparatus shown in FIG. 1 was stable against the cleaning process in oxygen plasma. Example 2 Au powder having an average particle size of 5 μm was mixed with borosilicate glass having an average particle size of 3 μm at a volume ratio of 30%, and acetone and PVB (polyvinyl butyral) resin were mixed in volume. 2% by weight. The resulting mixture was milled in a ball mill for 20 hours.

Next, the slurry obtained by the above-mentioned milling step was dried to completely remove acetone, and then pulverized by a grinder. A raw material powder for molding was obtained. Further, the obtained raw material powder was charged into a mold and pressed into a plate at a pressure of 5 MPa. The obtained plate-like molded body was 1000
After sintering in air for about 2 hours at
Calcination was performed at 950 ° C. for about 5 hours at a pressure of 2000 atm in an atmosphere of oxygen containing r10%. The obtained fired molded body was machined. The electrode member 22 described above with reference to FIG. 4 was obtained.

The obtained electrode member 22 is approximately 1 ×, which is suitable as an electrostatic deflector used in a charged particle beam exposure apparatus.
It showed a specific electric resistance of 10 ^-1 to 1 × 10 ^-2 Ωcm.
Further, since all of the electrode members were made of oxide and oxide glass, the charged particle beam exposure apparatus shown in FIG. 1 was stable against the cleaning treatment in oxygen plasma. Example 3 Pt powder having an average particle size of 1 μm, borosilicate glass powder having an average particle size of 2 μm, and softening point 11 having an average particle size of 3 μm
Aluminosilicate glass powder at 00 ° C is mixed at a volume ratio of 60%, 30% and 10%, respectively, and acetone and PVB (polyvinyl butyral) resin are added at a ratio of 2% by volume. did. The resulting mixture was milled in a ball mill for 20 hours.

Next, the slurry obtained by the above-mentioned milling step was dried to completely remove acetone, and then pulverized with a grinder. A raw material powder for molding was obtained. Further, the obtained raw material powder was charged into a mold and pressed into a plate at a pressure of 5 MPa. The obtained plate-like molded body was 1000
Calcination was performed in air at about 5 ° C. for about 5 hours. The obtained fired molded body was machined. The electrode member 22 described above with reference to FIG. 4 was obtained.

The obtained electrode member 22 is approximately 1 ×, which is suitable as an electrostatic deflector used in a charged particle beam exposure apparatus.
It showed a specific electric resistance of 10 ^-1 to 1 × 10 ^-2 Ωcm.
Further, since all of the electrode members were made of oxide and oxide glass, the charged particle beam exposure apparatus shown in FIG. 1 was stable against the cleaning treatment in oxygen plasma. Example 4 RuO ₂ powder having an average particle size of 0.1 μm and an average particle size of 2 μm
m SrRuO ₃ powder and Bi ₂ O ₃ having an average particle size of 2 μm
15%, 10% and 65% by volume of the powder, respectively
, And acetone and PVB (polyvinyl butyral) resin were added thereto at a volume ratio of 2%.
The resulting mixture was milled in a ball mill for 20 hours.

Next, the slurry obtained by the above-mentioned milling step was dried to completely remove acetone, and then pulverized by a grinder. A raw material powder for molding was obtained. Further, the obtained raw material powder was charged into a mold and pressed into a plate at a pressure of 5 MPa. The obtained plate-like molded body was 1000
Calcination was performed in air at about 5 ° C. for about 5 hours. The obtained fired molded body was machined. The electrode member 22 described above with reference to FIG. 4 was obtained.

The obtained electrode member 22 is about 1 ×, which is suitable as an electrostatic deflector used in a charged particle beam exposure apparatus.
It showed a specific electric resistance of 10 ^-1 to 1 × 10 ^-2 Ωcm.
Further, since this electrode member was entirely made of oxide, the charged particle beam exposure apparatus shown in FIG. 1 was stable against the cleaning process in oxygen plasma.

Table 1 below shows the results of Examples 1 to 4 described above.
1. The electrode member 22 manufactured in each of
The electrostatic deflector 20 in the electron beam exposure apparatus 10
When used on the substrate 13 to be processed.
Summary of drift amount (nm) after 10 seconds of irradiation
It is. Also, evaluate the resistance to oxygen plasma treatment.
For 2 minutes and 180 minutes
In each case, the amount of drift was measured. Furthermore, compare
In order to provide the electrode member 22, a conventional Al _Two O_Three ・
When using TiC (AlTiC) ceramic (Comparative Example)
1) A conventional AlTiC ceramic as the electrode member 22
Using a material covered with a 1μm Pt plating film
The measurement results of (Comparative Example 2) are also shown.

[0065]

[Table 1] As understood from the measurement results shown in Table 1, when a conventional AlTiC ceramic was used as an electrode material as in Comparative Example 1, the effect of the magnetism (0.005 emu / cm ³ ) of the AlTiC ceramic was used. Thus, the drift of the beam was observed from the initial stage of the electron beam irradiation. In addition, after the oxygen plasma irradiation, the AlTiC ceramic deteriorated and the insulation was caused. Therefore, the charge-up phenomenon significantly increased the beam drift amount to 1 μm or more.

Also, as in Comparative Example 2, Al with a Pt film
When the TiC ceramic was used, the initial beam drift was improved compared to Comparative Example 1 due to the influence of the Pt plating film. However, after oxygen plasma irradiation, P
Since the etching of the t-plated film occurred, a charge-up phenomenon caused by material deterioration occurred as in Comparative Example 1, and the drift amount of the beam increased with the irradiation time of the oxygen plasma.

In contrast to these undesirable consequences,
In each of Examples 1 to 4, a slight drift of the beam was observed at the initial stage of the electron beam irradiation. This is attributed to the contamination of the organic substance or the like attached to the surface of the electrode member, and is considered to be caused by charge-up and drift. However, after oxygen plasma irradiation, the amount of drift was significantly improved because these stains were removed. Further, the longer the irradiation time of the oxygen plasma, the smaller the amount of contamination on the member surface and the lower the drift amount.

To summarize the above results, the present invention
According to (Examples 1 to 4), by using the electrode member of the present invention as the electrostatic deflector 20 in the charged particle beam exposure apparatus 10 of FIG. 1, the specific electric resistance value of the electrode member is optimized and the electron beam The drawing speed of the exposure apparatus 10 can be improved. When the conventional electrode material is used, the drift amount after 10 seconds of electron beam irradiation increases remarkably with the increase in the plasma processing time, whereas when the electrode material according to the present invention is used, such a change is Not at all.
For example, in an AlTiC electrode, oxygen plasma irradiation 10
The electron beam drift amount after 1 second was 1 μm, but the drift amount when the electrode of the present invention was used was 10 nm or less.

Although the present invention has been described with reference to the preferred embodiments, the present invention is not limited to such specific embodiments, and various changes and improvements can be made within the spirit and scope of the appended claims. is there. Finally, preferred embodiments of the present invention are summarized below for a better understanding of the present invention.

(Supplementary Note 1) Main component is oxide ceramics
Conductive ceramic material, comprising RuO_Two , R
eO_Two , IrO_Two , SrVO_Three , CaVO_Three , LaTi
O_Three , SrMoO_Three , CaMoO_Three , SrCrO_Three , C
aCrO_Three , LaVO_Three , GdVO_Three , SrMnO_Three ,
CaMnO_Three , NiCrO_Three , BiCrO_Three , LaCr
O _Three , LnCrO_Three , SrRuO_Three , CaRuO_Three , S
rFeO_Three , BaRuO_Three, LaMnO_Three , LnMnO_Three
 , LaFeO_Three , LnFeO_Three , LaCoO_Three , La
RhO_Three , LaNiO_Three , PbRuO_Three , Bi_Two Ru_Two 
O₇ , LaTaO_Three, SrRuO_Three , PbRuO_Three as well as
BiRuO_ThreeAt least one selected from the group consisting of
Oxide particles and LiF, Li_Three PO_Four , Li_Two CO
_Three , Li_Two SO_Four , Bi_Two O_Three Oxidation containing Bi and Bi
Selected from the group consisting of oxides, complex oxides containing PbO and Pb
Formed from at least one type of auxiliary particles
A conductive ceramic material, characterized in that:

(Supplementary Note 2) A conductive ceramic material characterized by being formed from at least one kind of metal particles having resistance to oxidation and at least one kind of inorganic glass particles. (Supplementary note 3) The conductive ceramic material according to supplementary note 2, wherein the metal is Au, Pt, or a combination thereof.

(Supplementary Note 4) The above-mentioned inorganic glass has a temperature of 400 ° C.
4. The conductive ceramic material according to Supplementary Note 2 or 3, which has the above softening point. (Supplementary Note 5) The conductive ceramic material according to supplementary note 4, wherein the inorganic glass has a composition that does not substantially include a volatile metal element. (Supplementary note 6) The conductive ceramic material according to supplementary note 5, wherein the volatile metal element is lead.

(Supplementary note 7) The conductive ceramic material according to any one of Supplementary notes 1 to 6, wherein the conductive ceramic material has a coefficient of thermal expansion of 10 ^-5 / ° C or less. (Supplementary Note 8) The conductive ceramic material according to any one of Supplementary Notes 1 to 7, wherein the conductive ceramic material has a specific electric resistance value in a range of 1 × 10 ⁻⁴ to 1 × 10 ⁴ Ω · cm. (Supplementary Note 9) The conductive ceramic material according to any one of Supplementary Notes 1 to 8, wherein the conductive ceramic material has a form of a fired molded body.

(Supplementary Note 10) The conductive material according to Supplementary Note 9, wherein the raw material particles are compacted and fired, and then the obtained bulk body is machined into a predetermined shape. Ceramic materials. (Supplementary Note 11) The conductive ceramic material according to Supplementary Note 9, which is obtained by molding a raw material particle to obtain a molded body having a predetermined shape, and then firing the obtained molded body.

(Supplementary Note 12) The conductive ceramic material according to any one of Supplementary Notes 1 to 8, wherein the conductive ceramic material has a form of a coating covering the surface of the metal workpiece. (Supplementary Note 13) The conductive ceramic material according to Supplementary Note 12, wherein a metal workpiece having a predetermined shape is obtained, and a coating made of the raw material particles is applied to a surface of the metal workpiece.

(Supplementary Note 14) Any one of Supplementary Notes 1 to 13
An electrode component comprising the conductive ceramic material described in the above item. (Supplementary note 15) The electrode component according to supplementary note 14, wherein the electrode component is used in a magnetic field. (Supplementary Note 16) An electrostatic deflector used in a charged particle beam exposure apparatus, comprising a deflection electrode made of the conductive ceramic material according to any one of Supplementary Notes 1 to 13.

(Supplementary Note 17) Any one of Supplementary Notes 1 to 13
A stage member used for supporting a substrate to be processed in a charged particle beam exposure apparatus, the stage member being made of the conductive ceramic material described in the above item. (Supplementary Note 18) A vacuum chamber, a charged particle beam source provided in the vacuum chamber, a stage member provided in the vacuum chamber and adapted to carry a substrate to be processed, and An electromagnetic lens disposed between the charged particle beam source and the stage member; and an electrostatic deflector disposed between the charged particle beam source and the stage member in the vacuum chamber. A charged particle beam exposure apparatus, wherein the electrostatic deflector comprises a deflection electrode made of the conductive ceramic material according to any one of supplementary notes 1 to 13. apparatus.

(Supplementary Note 19) The supplementary note 1, wherein the stage member is further made of the conductive ceramic material according to any one of Supplementary notes 1 to 13.
9. A charged particle beam exposure apparatus according to item 8. (Supplementary Note 20) The inner wall of the vacuum chamber is further provided with additional notes 1 to 1.
20. A charged particle beam exposure apparatus according to claim 18 or 19, further comprising a liner made of the conductive ceramic material according to any one of (3) to (3).

[0079]

According to the present invention, the composite of the starting material has a specific electric resistance of about 10 ^-1 Ω · cm at room temperature, and its specific resistance is reduced by the oxygen plasma treatment. In addition, a conductive ceramic material whose surface is not adversely affected by the oxygen plasma treatment can be obtained. Further, when this ceramic material is used as an electrode material in a charged particle beam exposure apparatus, it is possible to simultaneously improve throughput and extend the life of the apparatus.

According to the present invention, 1 × 10 ⁻¹ at room temperature is used.
It has a specific electric resistance of about Ωcm, its specific resistance is not reduced by the oxygen plasma treatment, and its surface is not adversely affected by the oxygen plasma treatment. An electrode component useful as a deflection electrode can be obtained. Furthermore, according to the present invention, when mounted on a charged particle beam exposure apparatus, not only can the spot position of the beam be moved accurately and quickly, but also an improvement in throughput and a long life of the apparatus can be achieved at the same time. The resulting electrostatic deflector can be obtained.

Further, according to the present invention, it can be advantageously used for forming a fine resist pattern in the manufacture of a highly integrated semiconductor device or the like, and the throughput can be improved, and the electrostatic capacity can be increased for a long time. A charged particle beam exposure apparatus that does not require replacement of the deflector can be obtained. In addition, the conductive ceramic material of the present invention can be widely applied to not only deflection electrodes of an electrostatic deflector but also conductive members used in a magnetic field, such as a stage and a liner of a lens barrel.

[Brief description of the drawings]

FIG. 1 is a schematic view showing a preferred example of a charged particle beam exposure apparatus according to the present invention.

FIG. 2 is a perspective view showing a configuration of an electrostatic deflector used in the charged particle beam exposure apparatus of FIG.

FIG. 3 is a cross-sectional view of the electrostatic deflector of FIG. 2 taken along line III-III.

FIG. 4 is a perspective view showing a configuration of a deflection electrode used in the electrostatic deflector of FIGS. 2 and 3;

FIG. 5 is a flow sheet showing an example of the manufacturing process of the deflection electrode of the present invention.

FIG. 6 is a flow sheet showing another example of the manufacturing process of the deflection electrode of the present invention.

FIG. 7 shows another charged particle beam exposure apparatus according to the present invention.
It is a schematic diagram which shows one preferable example.

8 is a cross-sectional view showing a configuration of a stage member used in the charged particle beam exposure apparatus of FIG.

FIG. 9 is a schematic view showing still another preferred example of the charged particle beam exposure apparatus according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 ... Charged particle beam exposure apparatus 10A ... Barrel 10B ... Liner 11 ... Electron beam source 11B ... Immersion lens 12 ... Stage 13 ... Substrate 14A-14F ... Electromagnetic lens 16 ... Block mask 18 ... Electromagnetic deflector 19 ... Electrostatic Deflector 20 ... Electrostatic deflector 21 ... Insulating cylindrical member 22 ... Deflection electrode 23 ... Separation groove 30 ... Charged particle beam exposure device 39 ... Electrostatic deflector 40 ... Charged particle beam exposure device

Continued on the front page F term (reference) 2H097 CA16 LA10 4G030 AA02 AA08 AA09 AA10 AA11 AA13 AA15 AA16 AA19 AA21 AA22 AA23 AA25 AA26 AA27 AA28 AA29 AA35 AA36 AA37 AA40 AA41 AA43 5A03 5A03 5A03 5A03 5A03

Claims (10)

[Claims] 1. Conductivity mainly composed of oxide ceramics
Conductive ceramic material, RuO_Two , ReO_Two , IrO_Two , SrVO_Three , CaVO
_Three , LaTiO_Three , SrMoO_Three , CaMoO_Three , Sr
CrO_Three , CaCrO_Three , LaVO_Three , GdVO_Three , S
rMnO_Three , CaMnO_Three , NiCrO_Three , BiCrO
_Three , LaCrO _Three , LnCrO_Three , SrRuO_Three , Ca
RuO_Three , SrFeO_Three , BaRuO_Three, LaMnO
_Three , LnMnO_Three , LaFeO_Three , LnFeO_Three , La
CoO_Three , LaRhO_Three , LaNiO_Three , PbRuO
_Three , Bi_Two Ru_Two O₇ , LaTaO_Three, SrRuO_Three ,
PbRuO_Three And BiRuO_ThreeSelected from the group consisting of
At least one oxide particle, LiF, Li_Three PO_Four , Li_Two CO_Three , Li_Two SO_Four ,
Bi_Two O_Three , Bi-containing complex oxides, PbO and Pb
At least one selected from the group consisting of composite oxides
Characterized by being formed from a kind of auxiliary particles.
Conductive ceramic materials. 2. At least one which is resistant to oxidation.
A conductive ceramic material formed of particles of at least one kind of metal and particles of at least one kind of inorganic glass. 3. The conductive ceramic material according to claim 2, wherein the metal is Au, Pt, or a combination thereof. 4. The conductive ceramic material according to claim 2, wherein the inorganic glass has a softening point of 400 ° C. or higher. 5. The conductive ceramic material according to claim 1, which has a form of a fired molded body. 6. The metal workpiece has a form of a coating applied to the surface of the metal workpiece.
The conductive ceramic material according to any one of the above. 7. An electrode component comprising the conductive ceramic material according to claim 1. Description: 8. The electrode component according to claim 7, wherein the electrode component is used in a magnetic field. 9. An electrostatic deflector for use in a charged particle beam exposure apparatus, comprising a deflection electrode made of the conductive ceramic material according to claim 1. Description: . 10. A vacuum chamber; a charged particle beam source disposed in the vacuum chamber; a stage member disposed in the vacuum chamber and adapted to carry a substrate to be processed; An electromagnetic lens disposed between the charged particle beam source and the stage member, and an electrostatic deflector disposed between the charged particle beam source and the stage member in the vacuum chamber. A charged particle beam exposure apparatus comprising: a charged particle, wherein the electrostatic deflector comprises a deflection electrode made of the conductive ceramic material according to any one of claims 1 to 6. Beam exposure equipment.