JP2003243495A - Ceramic substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ceramic substrate which is excellent in temperature rise characteristics, dielectric strength and Young's modulus at a high temperature, and is optimum for a substrate for a semiconductor manufacturing/ inspecting device. <P>SOLUTION: In a ceramic substrate which has a conductor on the surface or inside thereof, the amount of a leak through the ceramic substrate is at most 10<SP>-7</SP>Pam<SP>3</SP>/sec(He) by measurement by a helium leak detector. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention mainly relates to the semiconductor industry.
Ceramic substrates used in
Pressure is high and semiconductor wafer
C has excellent adsorption capacity and a hot plate (heat
When used as a
Related to a lamic substrate. [0002] 2. Description of the Related Art Semiconductors are needed in various industries.
Semiconductor chips are, for example,
Slicing a silicon single crystal to a predetermined thickness
After fabricating EHA, multiple integration cycles
It is manufactured by forming a road or the like. In the manufacturing process of this semiconductor chip,
Etch a silicon wafer placed on an electrostatic chuck
And various processes such as CVD, conductor circuits and elements, etc.
To form At that time, gas for deposition, etchin
Since corrosive gases are used as
It is necessary to protect the electrostatic electrode layer from corrosion by
In addition, since it is necessary to induce suction force,
The layer is usually covered by a ceramic dielectric film or the like.
You. [0004] Conventionally, as this ceramic dielectric film,
Although nitride ceramics are used, for example,
No. 5-8140 discloses nitrides such as aluminum nitride.
An electrostatic chuck using the same is disclosed. Also, JP
Japanese Patent Application Laid-Open No. 9-48668 has an Al-ON structure.
A carbon-containing aluminum nitride is disclosed. [0005] However, these security measures
Electrostatic chucks using lamic have good temperature rise and fall characteristics.
Minutes, and at high temperatures the withstand voltage decreases or
With the problem that the rate decreases and warpage occurs
Was. Such problems are not limited to electrostatic chucks, but also
Surface of ceramic substrate such as plate and wafer prober
For semiconductor manufacturing / inspection with conductors formed inside
It turns out that it is seen on a ceramic substrate. [0006] Means for Solving the Problems The present inventors have set forth the above object.
As a result of intensive research to solve
Temperature rise / fall characteristics, withstand voltage and Young's modulus of the backing substrate, etc.
Was found to be due to insufficient sinterability
The degree of sintering is determined by a helium leak detector.
10 in the measurement^-7Pa ・ m^Three / Sec (He) or less
To solve the above problem.
It was newly found that it can be done. Specifically,
First, oxidize the surface of
Then, by adding oxide and performing pressure sintering,
The amount of leak is measured by the helium leak detector.
10^-7Pa ・ m^Three / Sec (He) or less
That the present invention has been completed
is there. In addition, by the measurement with the helium leak detector,
The leak amount is 10^-12 Pa ・ m^Three / Sec (He) or less
If the temperature is below, the densification proceeds too much and the fracture toughness
Also found that the thermal conductivity of the steel decreased.
Was. [0007] That is, the present invention is to
In the ceramic substrate on which the conductor is formed,
The ceramic substrate is measured with a helium leak detector.
Regularly 10^-7Pa ・ m^Three / Sec (He) or less
It is a ceramic substrate characterized by the following. The ceramic substrate of the present invention is a helium-free ceramic substrate.
The leak amount measured by the detector was 10^-7P
am^Three / Sec (He) or less. This degree of Lee
Above, the ceramic substrate is sintered sufficiently densely
Temperature rise and fall characteristics of the ceramic substrate and high temperature
Excellent in withstand voltage and Young's modulus. Therefore, the above ceramics
No warpage occurs in the substrate. When measuring the leak amount, a diameter 30
mm, area 706.5mm^Two , 1 mm thick,
Prepare a sample similar to that of the
To the detector. Then, pass through the sample
By measuring the helium flow rate,
It is possible to measure the leak amount of the work substrate. Helium re
Detector measures the partial pressure of helium at the time of the leak.
It does not measure the absolute value of the gas flow.
Preliminarily measure the helium partial pressure at the time of a known leak,
Simple proportionality of unknown leak rate from current helium partial pressure
Calculate by calculation. Detailed measurement of helium leak detector
The principle is “Monthly Semiconductor Wor
ld 1992.111 p112-115 ".
ing. That is, the above ceramic substrate is sufficiently dense
When sintering, the above leakage amount shows a fairly small value.
You. On the other hand, the sinterability of the ceramic substrate is insufficient.
And the leak amount shows a large value. In the present invention, for example, a nitride ceramic
First, oxidize the surface of the particles of the
Is added and sintering is performed under pressure.
A sintered body is formed in which the oxide layer and the added oxide are integrated
The sintered body is a helium leak detector
Measured by 10^-7Pa ・ m^Three / Sec (He) or less
An extremely small leak amount results. The amount of leak
1 × 10 as measured by um leak detector^-12 ~ 1 ×
10^-8Pa ・ m^Three / Sec (He) is good. Heat at high temperatures
This is because conductivity can be ensured. Incidentally, Japanese Patent Application Laid-Open No. 9-48668,
JP-A-9-48669, JP-A-10-72260
In some patent publications, there are nitrides with some ALON crystal phases.
Although a luminium sintered body is disclosed, a metal oxide is added.
It is not added, and is manufactured by the reduction nitriding method.
Comparative example with no oxygen on the surface and poor sinterability
10 as in^-6Pa ・ m^Three / Sec (He)
A relatively large leak amount occurs. JP-A-7-153
In Japanese Patent No. 820, yttria is added.
Because the surface of aluminum nitride raw material powder is fired
However, as is clear from the comparative example, the sinterability was poor.
10 as in the comparative example^-6Pa ・ m^Three / Sec (H
A relatively large leak amount as shown in e) occurs. JP
No. 5-36819 discloses that silicon nitride and yttria,
Shows electrostatic chuck using sintered body using Lumina
However, the introduction or introduction of oxygen into the raw material is not described or suggested.
This is also 10^-6Pa ・ m^Three / Sec (He)
Such a relatively large leak amount occurs. Further, JP
In Japanese Patent Application Laid-Open No. Hei 10-279359, low-temperature, normal-pressure firing is used.
Therefore, the amount of leak also increases. In addition, Japanese Patent Application Laid-Open
Japanese Patent Application Laid-Open No. 158002 discloses A used for a semiconductor mounting substrate.
1N substrate, semiconductor manufacturing / inspection apparatus as in the present invention
It is not used for Also, JP-A-10-16785
In Japanese Patent Publication No. 9, the amount of yttria is as low as 0.2% by weight,
Since the sinterability is not sufficient, the leak amount also increases.
Thus, in the prior art, helium as in the present invention is used.
Leakage is 1 × 10^-7 Pa ・ m^Three / Sec (He) or less
Semiconductor manufacturing and inspection using sintered body that can be adjusted below
The device has not been realized. The oxide to be added is a nitride ceramic
Is preferably an oxide of an element constituting Nitride
Identical to ceramic surface oxide layer and extremely sintered
This is because it is easy to make it. Acidize nitride ceramic surface
To be converted to 500 to 1000 in oxygen or air.
It is desirable to heat at 0.5C for 0.5 to 3 hours. Also, a nitride ceramic used for sintering is provided.
The average particle diameter of the powder is preferably about 0.1 to 5 μm.
No. This is because sintering is easy. Furthermore, the content of Si
Is 0.05 to 50 ppm, and the content of S is 0.05 to 80.
ppm (all by weight) is desirable. these
Is the oxide film on the nitride ceramic surface and the added oxide
This is because they are considered to be combined. Other firing conditions
Will be described later in the manufacturing method of the electrostatic chuck.
I do. It is obtained by performing calcination using the above method.
The ceramic substrate used is 0.05 to 10% by weight of oxygen.
It is desirable to contain. Less than 0.05% by weight
Means that sintering does not proceed, fracture occurs at the grain boundaries, and thermal conductivity
If the oxygen content exceeds 10% by weight, the acid
Element segregates at the particle boundary, causing fracture at the particle boundary,
This is because the conductivity is lowered and the temperature raising / lowering characteristics are lowered. In the present invention, the ceramic substrate contains oxygen.
It is made of nitride ceramic having
It is desirable that the pore diameter is 50 μm or less, and the porosity is
5% or less is desirable. In addition, the ceramic substrate includes
If there are no pores or if there are pores,
The pore diameter of the maximum pore is desirably 50 μm or less.
No. When no pores exist, the withstand voltage at high temperature
Is particularly high, and conversely, if pores are present, the fracture toughness
The value increases. Or to either of the design for this purpose, request
It depends on the characteristics. Destroyed by the presence of pores
The reason for the increase in toughness is not clear, but
Presumably because the expansion is stopped by stomata
You. In the present invention, when the maximum pore diameter is 50 μm or less,
Desirably, if the pore size exceeds 50 μm
Ensure withstand voltage characteristics at high temperatures, especially at 200 ° C or higher
Is difficult. The maximum pore size is 10μ
m or less is desirable. Less warpage at 200 ° C or higher
This is because that. The porosity and the maximum pore diameter are determined by the sintering process.
Adjust by pressure time, pressure, temperature, additives such as SiC and BN
I do. Pores are introduced to prevent sintering of SiC and BN
Can be done. When measuring the pore diameter of the maximum pore,
Are prepared, and the surfaces thereof are mirror-polished, and 2000 to 50
The surface is photographed at 10 times with an electron microscope at a magnification of 00 times.
Then, the largest pore size was selected from the photographed photos, and
The average of the peaks is defined as the maximum pore diameter. The porosity is measured by the Archimedes method.
You. Pulverized sintered body and pulverized in organic solvent or mercury
Put the material in, measure the volume, and calculate the true ratio from the weight and volume of the pulverized material.
Weight and calculate the porosity from the true specific gravity and the apparent specific gravity.
Because The diameter of the ceramic substrate of the present invention is 200 m.
m or more is desirable. Especially 12 inches (300mm) or more
It is desirable that Next-generation semiconductor wafer mainstream
Because it becomes. In addition, the present invention solves the problem of warpage.
Occurs on a ceramic substrate with a diameter of 200 mm or less.
Because it is difficult. The thickness of the ceramic substrate of the present invention is 50 m
m or less, particularly preferably 25 mm or less. Sera
If the thickness of the mix substrate exceeds 25 mm,
The heat capacity of the plate may be too large.
When heating and cooling with steps, due to the large heat capacity
This is because the temperature followability may be reduced.
In addition, the problem of warping solved by the present invention is that the thickness is 25 mm.
Hardly to occur with thick ceramic substrates exceeding
It is. The thickness of the ceramic substrate is especially 5mm or less.
Optimal. The thickness is desirably 1 mm or more. Ma
Further, the ceramic substrate of the present invention is desirably at least 150 ° C.
Is used at 200 ° C. or higher. The ceramic constituting the ceramic substrate of the present invention.
The material of the ceramic is not particularly limited, but may be a nitride ceramic or a ceramic.
And carbide ceramics are preferred. The above nitride ceramic
As a metal nitride ceramic, for example, aluminum nitride
, Silicon nitride, boron nitride, titanium nitride, etc.
Can be Further, as the above-mentioned carbide ceramic, for example,
For example, silicon carbide, titanium carbide, tantalum carbide, tan carbide
Gustene, zirconium carbide and the like. Also on
Oxide ceramic may be used as the ceramic material.
The above-mentioned oxide ceramics include metal oxide ceramics.
For example, alumina, zirconia, cordurai
And mullite. Among these nitride ceramics, in particular,
Aluminum nitride is preferred. Thermal conductivity 180W / m
-Because it is the highest, K. In the present invention, the acid is added to the ceramic substrate.
It is desirable to contain a compound. As the above oxide
Is, for example, an alkali metal oxide, an alkaline earth metal acid
And rare earth oxides can be used.
Among the binders, in particular, CaO, Y_Two O_Three , Na_Two O,
Li_Two O, Rb_Two O is preferred. In addition, alumina, silicon
Mosquitoes may be used. As the content of these, 0.5
-20% by weight is desirable. If less than 0.5% by weight,
10^-7Pa ・ m^Three / Sec (He) or less
Sometimes. As the oxide to be added, a silicon nitride
In this case, silica is most suitable. According to the present invention, 5 to 50 ceramic substrates are used.
Desirably, it contains 00 ppm of carbon.
The inclusion of carbon makes the ceramic substrate black
Can be colored, radiant heat when used as a heater
Can be fully utilized. carbon
Is amorphous or crystalline
Good. If amorphous carbon is used,
Can be prevented from lowering the volume resistivity
If used, the thermal conductivity decreases at high temperatures
Is prevented. Therefore, depending on the application
Means that both crystalline and amorphous carbon
You may use together. The carbon content is 50 to 2
000 ppm is more preferred. A place where the ceramic substrate contains carbon.
In that case, the brightness shall be based on the provisions of JIS Z 8721.
Carbon should be contained so that the value is less than N4
Is desirable. The one with this level of lightness is the amount of radiant heat,
This is because the concealing property is excellent. Here, the lightness N is an ideal black lightness.
0, the ideal white lightness is 10, and these black light
Between the brightness and the brightness of white, the perception of the brightness of the color is equal
Each color is divided into 10 so that
It is displayed. The actual measurement of lightness is N0 to N1
The comparison is made with the color chart corresponding to 0. Decimal point 1 in this case
The place is 0 or 5. [0029] DESCRIPTION OF THE PREFERRED EMBODIMENTS The ceramic substrate of the present invention
Used in equipment for manufacturing bodies and inspecting semiconductors
It is a ceramic substrate.
For example, electrostatic chuck, wafer prober, hot plate
(Ceramic heater), susceptor and the like. The conductor formed inside the ceramic substrate is
When the electric body is a resistance heating element, a ceramic heater
(Hot plate). FIG.
Is a ceramic substrate according to an embodiment of the present invention.
FIG. 2 is a plan view schematically showing an example of a cook heater, and FIG.
Is a partially enlarged view showing a part of the ceramic heater shown in FIG.
It is a large sectional view. The ceramic substrate 11 is formed in a disk shape.
The temperature control means is provided inside the ceramic substrate 11.
The resistance heating element 12 as a step is formed in a concentric pattern
Have been. These resistance heating elements 12 are close to each other.
Double concentric circles form a single line as a set of circuits.
And input and output terminals at both ends of the circuit.
External terminal 13 is connected through a through hole 19.
ing. Further, as shown in FIG.
11 is provided with a through hole 15, which is supported by the through hole 15.
The pins 26 are inserted and the silicon wafer 9 is held.
You. By moving the support pins 26 up and down,
Receiving the silicon wafer 9 from the
Is placed on the wafer processing surface 11a of the ceramic substrate 11.
And heat the silicon wafer 9 to the wafer processing surface 11a.
Support at a certain distance from the
can do. Also, the bottom surface 1 of the ceramic substrate 11
1b has a bottomed hole for inserting a temperature measuring element such as a thermocouple.
14 are provided. Then, the resistance heating element 12 is energized.
Then, the ceramic substrate 11 is heated, whereby the ceramic substrate 11 is heated.
An object to be heated such as a recon wafer can be heated. The ceramic constituting this hot plate
The substrate 11 was measured by a helium leak detector.
The leak amount is 10^-7Pa ・ m^Three / Sec (He) or less
The ceramic substrate 11 is sufficiently dense
Tied. Therefore, this ceramic substrate 11
Excellent temperature-lowering characteristics, withstand voltage and Young's modulus decrease at high temperatures.
No warpage occurs on the ceramic substrate.
No. The resistance heating element is provided inside the ceramic substrate.
And may be provided on the bottom surface of the ceramic substrate. Usually
When providing an anti-heating element, support the ceramic substrate
A blowing port for air or other refrigerant as a cooling means
And the like may be provided. Resistance heating element inside ceramic substrate
When it is provided in a part, a plurality of layers may be provided. in this case
The patterns of each layer are formed to complement each other
When viewed from the heating surface, a pattern is formed on some layer
Is desirable. For example, the staggered arrangement
Structure. As the resistance heating element, for example, metal or
Sintered conductive ceramics, metal foils, metal wires, etc.
It is. Tungsten, molybdenum
At least one selected from These metals
Is relatively resistant to oxidation and has sufficient resistance to generate heat
This is because that. As the conductive ceramic, a tongue is used.
At least one selected from carbides of stainless steel and molybdenum
Seeds can be used. In addition, ceramic substrates
When forming a resistance heating element on the bottom, use a metal sintered body.
Noble metals (gold, silver, palladium, platinum), nickel
It is desirable to use Specifically, silver, silver-palladium
For example. Used for the above metal sintered body
The metal particles used are spherical, scaly, or spherical.
A flaky mixture can be used. Forming a resistance heating element on the surface of a ceramic substrate
When sintering, metal oxides may be added to the metal and sintered.
No. The above metal oxides are used for ceramic substrates and
This is for bringing the metal particles into close contact. By the above metal oxide
Improves the adhesion between the ceramic substrate and the metal particles
Although the reason is not clear, the surface of the metal particles is slightly oxidized
When the film is formed and the ceramic substrate is an oxide
Of course, even if it is a non-oxide ceramic, its surface
Is formed with an oxide film. Therefore, this oxide film
Sintering on ceramic substrate surface via metal oxide
And the metal particles do not adhere to the ceramic substrate
It is thought. As the metal oxide, for example, oxidized
Lead, zinc oxide, silica, boron oxide (B _Two O_Three ), Al
At least one selected from Mina, Yttria and Titania
Species are preferred. These oxides have the resistance value of the resistance heating element.
Between the metal particles and the ceramic substrate without increasing the
This is because adhesion can be improved. The metal oxide is 100 parts by weight of metal particles.
0.1 parts by weight or more and less than 10 parts by weight
desirable. By using a metal oxide in this range,
Resistance value does not become too large, metal particles and ceramic substrate
This is because the adhesiveness with the adhesive can be improved. In addition, lead oxide, zinc oxide, silica,
Udine (B_Two O_Three ), Alumina, yttria, titania
The ratio is based on 100 parts by weight of the total amount of the metal oxide.
1 to 10 parts by weight of lead oxide and 1 to 30 parts by weight of silica
Parts, 5 to 50 parts by weight of boron oxide, 20 to 7 parts of zinc oxide
0 parts by weight, 1-10 parts by weight of alumina, 1 part of yttria
-50 parts by weight and titania of 1-50 parts by weight are preferred.
However, the total amount of these should not exceed 100 parts by weight.
It is desirable to be adjusted. These ranges are particularly
This is because the adhesiveness to the substrate can be improved. A resistance heating element is provided on the bottom surface of the ceramic substrate.
In this case, the surface of the resistance heating element 25 is covered with a metal layer 25a.
Desirably, it is covered (see FIG. 5). Resistance heating element
Reference numeral 25 denotes a sintered body of metal particles, which is oxidized when exposed.
The oxidation easily changes the resistance value. So
Here, by coating the surface with the metal layer 25a,
Can be prevented. The thickness of the metal layer 25a is 0.1 to 100 μm.
m is desirable. Do not change the resistance of the resistance heating element.
Is within the range that can prevent oxidation of the resistance heating element
It is. The metal used for coating is a non-oxidizing metal
I just need. Specifically, gold, silver, palladium, platinum,
At least one selected from nickel is preferred.
Of these, nickel is more preferred. The resistance heating element
A terminal is required to connect to the
Attached to the resistance heating element through the field, but nickel is solder
This is because the thermal diffusion of the metal is prevented. The connection terminal
External terminals made of metal can be used. Note that the resistance heating element is placed inside the ceramic substrate.
If formed, the surface of the resistance heating element may be oxidized.
There is no need for coating. Resistance heating element inside heater plate
If it is formed in the part, the surface of the resistance heating element
It may be. Using a metal foil or a metal wire as the resistance heating element
You can also. Nickel foil, stainless steel
Resistive heat generated by patterning of stainless steel foil by etching etc.
A body is desirable. Patterned metal foil
You may bond with a fat film etc. As a metal wire,
For example, tungsten wire, molybdenum wire, etc.
You. The conductor formed inside the above ceramic substrate
If the conductor is an electrostatic electrode layer, the ceramic substrate
Can be used as an electrostatic chuck. This place
If the RF electrode or heating element is below the electrostatic
It may be formed as a conductor in the mix substrate. Figure
3 schematically shows an embodiment of the electrostatic chuck according to the present invention.
FIG. 4 is a longitudinal sectional view shown in FIG.
It is an AA line sectional view in a jack. In this electrostatic chuck 101, a disk-shaped
A chuck positive electrode electrostatic layer 2 and a chip
The electrostatic electrode layer composed of the negative electrode electrostatic layer 3 is buried.
And a thin ceramic layer 4 (hereinafter referred to as “layer 4”)
Below, referred to as a ceramic dielectric film). Ma
The silicon wafer 9 is placed on the electrostatic chuck 101.
And grounded. As shown in FIG. 4, the chuck positive electrode electrostatic layer
2 comprises a semicircular arc-shaped portion 2a and a comb tooth portion 2b,
The negative electrode electrostatic layer 3 also has a semicircular portion 3a and a comb-tooth portion 3b.
These chuck positive electrode electrostatic layer 2 and chuck
The negative electrode electrostatic layer 3 intersects the comb teeth 2b, 3b.
These chuck positive electrode electrostatic layers 2 and
The DC power supply +
Side and-side are connected, and the DC voltage V_Two Is applied
It has become. The inside of the ceramic substrate 1 is
To control the temperature of the con-wafer 9, FIG.
A resistance heating element 5 having a concentric circular shape in plan view as shown is provided.
External terminals are connected to both ends of the resistance heating element 5,
Fixed, voltage V₁ Is applied. Figure
Although not shown in 3 and 4, this ceramic substrate 1
Is for inserting a temperature measuring element as shown in FIGS.
To support the bottomed hole and the silicon wafer 9 up and down
A through hole for inserting a pin (not shown) is formed
I have. The resistance heating element is formed on the bottom of the ceramic substrate.
May be implemented. When the electrostatic chuck 101 is operated,
Is applied to the chuck positive electrostatic layer 2 and the chuck negative electrostatic layer 3.
DC voltage V_Two Is applied. This allows the silicon wafer
Reference numeral 9 denotes a chuck positive electrostatic layer 2 and a chuck negative electrostatic layer 3.
These electrodes have a ceramic dielectric due to the electrostatic action of
It is adsorbed and fixed via the membrane 4. This
Thus, the silicon wafer 9 is fixed on the electrostatic chuck 101.
After that, the silicon wafer 9 is subjected to various processes such as CVD.
Is performed. In the electrostatic chuck 101, a ceramic
The dielectric film 4 is made of a nitride ceramic containing oxygen.
In addition, the porosity is 5% or less, and the maximum pore diameter is 5%.
It is desirable that the thickness be 0 μm or less. Also, this ceramic
The pores in the dielectric film 4 are independent of each other.
It is desirable to be configured. This electrostatic chuck is
The formed ceramic substrate is used for helium leak detector.
Measurement, the leak amount was 10^-7Pa ・ m^Three / Se
c (He) or less, the ceramic substrate is sufficiently
It is densely sintered. Therefore, this ceramic substrate
Excellent temperature rise and fall characteristics, withstand voltage and Young's modulus decrease at high temperature
And the ceramic substrate may be warped.
Absent. As the temperature control means, the resistance heating element 12
Another example is a Peltier element (see FIG. 7). temperature
If a Peltier element is used as the control means,
Both heat generation and cooling by changing the flow direction
This is advantageous because Peltier element 8 is shown in FIG.
As shown, p-type and n-type thermoelectric elements 81 are connected in series,
By joining this to a ceramic plate 82 or the like,
Is done. Examples of Peltier devices include silicon
Germanium, bismuth / antimony, lead / tellurium
And the like. The electrostatic chuck of the present invention is, for example, shown in FIG.
4 has a configuration as shown in FIG. ceramic
The material of the substrate has already been described,
The other components constituting the electrostatic chuck,
And for other embodiments of the electrostatic chuck of the present invention,
It will be described in detail sequentially. Ceramic used in the electrostatic chuck of the present invention
The dielectric film is preferably made of a nitride ceramic.
New As the nitride ceramic, the ceramic
The same thing as a substrate is mentioned. The above nitride ceramic
Preferably contains oxygen. In this case,
Sintering tends to proceed in
The pores become independent pores even when
Voltage is improved. Making the above nitride ceramic contain oxygen
Therefore, metal oxides are usually
The materials are mixed and fired. As the above metal oxide,
Lumina (Al_Two O_Three ), Silicon oxide (SiO_Two ) Etc.
Can be The amount of addition of these metal oxides is
0.5 to 10 parts by weight with respect to 100 parts by weight
New The thickness of the ceramic dielectric film is set to 50 to 50.
By setting it to 00 μm, it is sufficient without lowering the chucking force.
High withstand voltage can be ensured. Above ceramic dielectric
If the thickness of the body film is less than 50 μm, the film thickness is too thin.
The silicon wafer is not placed.
The dielectric breakdown of the ceramic dielectric film
On the other hand, the thickness of the ceramic dielectric film is 50
If it exceeds 00 μm, the distance between the silicon wafer and the electrostatic electrode
The ability to adsorb silicon wafers is low due to separation
It will get worse. The thickness of the ceramic dielectric film is 100
〜1500 μm is preferred. The porosity of the ceramic dielectric film is 5%
Hereinafter, the pore diameter of the maximum pore is preferably 50 μm or less.
When the porosity exceeds 5%, the number of porosity increases,
Also, the pore diameter becomes too large, and as a result,
It becomes easier to pass. Ceramic dielectric film having such a structure
Then, the withstand voltage decreases. In addition, the maximum pore
If the pore size exceeds 50 μm, oxides will be present at the grain boundaries.
However, the withstand voltage at a high temperature cannot be secured. The porosity is
0.01-3% is preferable, and the pore diameter of the maximum pore is 0.1%.
1 to 10 μm is preferred. Ceramic with such a configuration
For dielectric films, measurement with a helium leak detector
And the leak amount is 10^-7Pa ・ m^Three / Sec (H
e) It is small as follows. Therefore, the ceramic dielectric film is sufficient
Sintering, and corrosive gas etc.
It does not permeate the electrostatic film and corrode the electrostatic electrodes.
No. In the ceramic dielectric film, carbon
Should be contained at 50 to 5000 ppm.
No. Hiding the electrode pattern provided in the electrostatic chuck
This is because high radiant heat can be obtained.
In addition, the lower the volume resistivity, the lower the
The suction capacity of the con-wafer is increased. In the present invention, in the ceramic dielectric film,
It is said that some pores may exist
This is because the toughness value can be increased,
Thermal shock resistance can be improved. As the above-mentioned electrostatic electrode, for example, a metal or
Is a conductive ceramic sintered body, a metal foil, or the like.
The metal sintered body is selected from tungsten and molybdenum.
It is preferable to use at least one of these. Metal foil
Also, it is desirable to be made of the same material as the metal sintered body. This
These metals are relatively hard to oxidize and have sufficient conductivity as electrodes.
This is because it has electrical conductivity. In addition, conductive ceramic
Selected from tungsten and molybdenum carbide
At least one can be used. FIGS. 9 and 10 show another electrostatic chuck.
FIG. 2 is a horizontal sectional view schematically showing an electrostatic electrode in FIG.
In the electrostatic chuck 20 shown in FIG.
The semi-circular chuck positive electrode electrostatic layer 22 and the chuck negative electrode
An electrostatic layer 23 is formed, and the electrostatic chuck shown in FIG.
The shape of a circle divided into four inside the ceramic substrate 1
Chuck positive electrode electrostatic layers 32a and 32b and chuck negative electrode
Electric layers 33a and 33b are formed. Also, two positive
Electrostatic layers 22a and 22b and two chuck negative electrodes
The layers 33a and 33b are formed so as to cross each other.
ing. In addition, the electrode of the form in which the electrode such as a circle is divided
When forming, the number of divisions is not particularly limited and is not more than 5 divisions.
The shape may be above, and the shape is not limited to the fan shape. Examples of the electrostatic chuck according to the present invention include:
For example, as shown in FIG.
Between the chuck positive electrode electrostatic layer 2 and the chuck dielectric film 4
A negative electrode electrostatic layer 3 is provided inside the ceramic substrate 1.
Denotes an electrostatic chuck 10 having a configuration in which a resistance heating element 5 is provided.
1. As shown in FIG. 5, a ceramic substrate 1 and a ceramic
A chuck positive electrode electrostatic layer 2 and a chuck negative electrode
An extremely electrostatic layer 3 is provided on the bottom surface of the ceramic substrate 1.
An electrostatic chuck 201 having a configuration in which the anti-heating element 25 is provided,
As shown in FIG. 6, the ceramic substrate 1 and the ceramic dielectric
Between the chuck positive electrode electrostatic layer 2 and the chuck negative electrode
And an electric layer 3, and a resistor is generated inside the ceramic substrate 1.
An electrostatic chuck 3 having a structure in which a metal wire 7 as a heat body is embedded.
01, as shown in FIG.
Between the chuck positive electrode electrostatic layer 2 and the chuck dielectric film 4
A negative electrode electrostatic layer 3 is provided on the bottom surface of the ceramic substrate 1.
Peltier element composed of thermoelectric element 81 and ceramic plate 82
8 is formed.
You. In the present invention, as shown in FIGS.
Chuck between the ceramic substrate 1 and the ceramic dielectric film 4
A positive electrode electrostatic layer 2 and a chuck negative electrode electrostatic layer 3 are provided,
The resistance heating element 5 and the metal wire 7 are formed inside the ceramic substrate 1.
To connect these to external terminals.
Connection portions (through holes) 16 and 17 are required. S
The through holes 16 and 17 are made of tungsten paste, moly
Refractory metals such as budene paste, tungsten carbide
Conductive ceramics such as sulfides and molybdenum carbide
It is formed by filling. The connecting portions (through holes) 16 and 17
Is preferably 0.1 to 10 mm. To prevent disconnection
In addition, cracks and distortion can be prevented. This
External terminals 6 and 18 are connected using the through holes as connection pads
(See FIG. 8D). The connection is made by solder or brazing material. Brazing material
Silver, palladium, aluminum,
Use gold brazing. Au-Ni alloy is
desirable. Au-Ni alloy has good adhesion to tungsten
It is because it is excellent. The ratio of Au / Ni is [81.5-82.
5 (% by weight)] / [18.5 to 17.5 (% by weight)]
desirable. The thickness of the Au—Ni layer is 0.1 to 50 μm.
desirable. This is because the range is sufficient to secure the connection.
Also, 10^-6-10^-Five500-1000 at high vacuum of Pa
When used at high temperature of ℃, Au-Cu alloy deteriorates,
An Au-Ni alloy is advantageous without such deterioration.
The total amount of impurity elements in the Au—Ni alloy is 100%.
It is desirable that the amount be less than 1 part by weight when
No. In the present invention, if necessary, a ceramic base may be used.
A thermocouple can be embedded in the bottomed hole of the plate. heat
Measure the temperature of the resistance heating element with a
The temperature can be controlled by changing the voltage and current
This is because that. The size of the junction of the thermocouple metal wire is
Same or larger than the wire diameter of each metal wire
And 0.5 mm or less. With this configuration
Therefore, the heat capacity of the joint becomes small,
In addition, it is quickly converted to a current value. For this reason,
Improved temperature control and small temperature distribution on the heated surface of the wafer
It will be. As the thermocouple, for example, JIS
-C-1602 (1980).
Type, R type, B type, S type, E type, J type, T type thermocouple
Can be FIG. 11 shows the static electricity of the present invention having the above configuration.
FIG. 4 schematically shows a support container 41 for fitting an electric chuck.
FIG. The support container 41 includes the electrostatic chuck 1
01 is fitted through the heat insulating material 45
You. The support container 11 also has a refrigerant outlet 42.
Is formed, and the refrigerant is blown from the refrigerant inlet 44.
From the suction port 43 to the outside through the refrigerant outlet port 42.
The refrigerant, and by the action of this refrigerant,
The electric chuck 101 can be cooled
I have. Next, the ceramic substrate of the present invention is an example.
FIGS. 8A to 8D show an example of a method for manufacturing an electrostatic chuck.
Explanation will be made based on the cross-sectional view shown in FIG. (1) First, nitride ceramic, carbide ceramic, etc.
Ceramic powder mixed with binder and solvent
The lean sheet 50 is obtained. As the ceramic powder described above
For example, by firing in an oxidizing atmosphere.
Use aluminum nitride powder containing
Can be In addition, if necessary,
A sintering aid such as c may be added. It should be noted that an electrostatic electrode layer printed body 51 described later has a shape.
Several or one sheets to be laminated on the formed green sheet
Green sheet 50 ′ becomes the ceramic dielectric film 4.
This is a separate layer from the ceramic substrate, if necessary.
It may be a composition. Usually, the raw material of the ceramic dielectric film 4
And the same material for the ceramic substrate 1
Is desirable. These are often sintered together.
This is because the firing conditions are the same. However, the material
If the materials are different, manufacture the ceramic substrate first.
Previously, an electrostatic electrode layer is formed on it, and
A ceramic dielectric film can also be formed. The binder used is an acrylic binder.
, Ethyl cellulose, butyl cellosolve, polyvinyl alcohol
At least one selected from alcohols is desirable.
Further, as the solvent, α-terpineol, glycol
At least one member selected from the group consisting of Mix these
The paste obtained by combining is sheeted by the doctor blade method.
The green sheet 50 is formed by molding into a shape. If necessary, a green sheet 50
Fill the through-hole and thermocouple for inserting the support pins of the con-wafer
Through-holes in the recesses, through-holes, etc.
I can keep it. Through holes are made by punching
Can be formed. Green sheet 50 thickness
Is preferably about 0.1 to 5 mm. Next, a conductor is inserted into the through hole of the green sheet 50.
Fill the paste and paste the through-hole prints 53, 54
Then, on the green sheet 50, an electrostatic electrode layer or a resistor
Print conductor paste to be heated. Printing is green
A desired aspect ratio is obtained in consideration of the contraction rate of the sheet 50.
So that the electrostatic electrode layer printed body 51,
The resistance heating element layer printed body 52 is obtained. Printed material is conductive ceramic
Print conductive paste containing mic, metal particles, etc.
It forms by doing. The conductivity contained in these conductive pastes
Tungsten or molybdenum as the conductive ceramic particles
The carbides of den are optimal. Hard to oxidize, thermal conductivity
This is because it is hard to lower. Examples of metal particles include
For example, tungsten, molybdenum, platinum, nickel, etc.
Can be used. Average particle size of conductive ceramic particles and metal particles
The diameter is preferably 0.1 to 5 μm. These particles are large
It is difficult to print conductor paste even if it is too small or too small
Because. Such pastes include metal particles and the like.
85 to 97 parts by weight of conductive ceramic particles, acrylic
System, ethyl cellulose, butyl cellosolve and polyvinyl chloride
At least one binder selected from nyl alcohol
1.5 to 10 parts by weight, α-terpineol, glyco
Water, ethyl alcohol and butanol.
Prepared by mixing 1.5 to 10 parts by weight of at least one solvent
The best paste for conductors. Next, as shown in FIG.
A green sheet 50 having 1, 52, 53, 54;
A green sheet 50 'having no printed body is laminated.
Green sheet 5 having no printed body on the side where the resistance heating element is formed
When laminating 0 ', the end face of the through hole is exposed,
Prevents oxidation during firing for forming resistance heating element
To do that. If the end of the through hole is exposed
If firing for forming a resistance heating element is performed, nickel
It is necessary to sputter metals that are difficult to oxidize, such as
More preferably, it is coated with Au-Ni gold brazing.
Is also good. (2) Next, as shown in FIG.
Heat and pressurize the layered body,
The electric paste is sintered. Heating temperature is 1700-20
00 ° C, pressurization is 100-200kgf / cm^Two Is preferred
These heating and pressurizing are performed under an inert gas atmosphere.
Do. Uses inert gas such as argon and nitrogen
can do. In this step, the through holes 16, 1
7, chuck positive electrode electrostatic layer 2, chuck negative electrode electrostatic layer 3, resistance
The anti-heating element 5 and the like are formed. (3) Next, as shown in FIG.
Bag holes 35 and 36 are provided for connection of external terminals. Blind hole 3
The inner walls of 5, 36 have at least a portion thereof conductive.
The inner wall that has been made conductive is the chuck positive electrostatic layer 2,
Connected to the negative electrode electrostatic layer 3, the resistance heating element 5, etc.
Is desirable. (7) Finally, as shown in FIG.
External terminals 6 and 18 are set in blind holes 35 and 36 via gold brazing.
I can. In addition, if necessary, a bottomed hole is provided
A thermocouple can be embedded in the Solder is silver-lead, lead-
Alloys such as tin and bismuth-tin can be used
You. The thickness of the solder layer is desirably 0.1 to 50 μm.
No. Because it is a range enough to secure the connection by solder
You. In the above description, the electrostatic chuck 101
(See FIG. 3), the electrostatic chuck 201 (see FIG.
), A ceramic with an electrostatic electrode layer
After manufacturing the metal plate, a conductive paper is placed on the bottom of this ceramic plate.
The strike is printed and fired to form a resistance heating element 25,
Then, the metal layer 25a may be formed by electroless plating or the like.
No. Further, the electrostatic chuck 301 (see FIG. 6) is manufactured.
If metal foil and metal wire in ceramic powder
Or a resistance heating element and embedded and sintered. Further
To manufacture the electrostatic chuck 401 (see FIG. 7)
After manufacturing a ceramic plate with an electrostatic electrode layer,
Peltier element is connected to a ceramic plate via a sprayed metal layer.
It should just match. Surface and Inside of the Ceramic Substrate of the Present Invention
Conductors are disposed on the surface, and the conductor layer on the surface is
Body layer, the inner conductor is guard electrode or ground
If at least one of the electrodes is
The lamic substrate functions as a wafer prober. FIG. 12 shows a wafer prober according to the present invention.
FIG. 13 is a sectional view schematically showing the embodiment, and FIG.
FIG. 2 is a sectional view taken along line AA of the wafer prober shown in FIG.
You. In this wafer prober 501, a disc-shaped ceramic
A groove 67 having a concentric circular shape in plan view is formed on the surface of the backing board 63.
And a silicon wafer is sucked into a part of the groove 67.
Are provided with a plurality of suction holes 68.
Most of the ceramic substrate 63 including
Chuck top conductor layer 62 for connecting to electrodes is circular
It is formed in a shape. On the other hand, the bottom of the ceramic
In order to control the temperature of the recon wafer,
A heating element 61 having a concentric circular shape in plan view as shown is provided.
External terminals (not shown) are provided at both ends of the heating element 61.
Is connected and fixed. In addition, the ceramic substrate 63
Inside, to remove stray capacitors and noise
A guard electrode 65 and a ground electrode 66 having a lattice shape in plan view
(See FIG. 13). Guard electrode 65
The material of the ground electrode 66 may be the same as that of the electrostatic electrode.
No. The thickness of the chuck top conductor layer 62 is
1 to 20 μm is desirable. If it is less than 1 μm, the resistance value is
Does not work as an electrode because it is too large, on the other hand, exceeds 20 μm
Is easy to peel due to the stress of the conductor and the conductor
It is. As the chuck top conductor layer 62, for example,
For example, copper, titanium, chromium, nickel, precious metals (gold, silver,
Refractory metals such as platinum, tungsten, and molybdenum
It is possible to use at least one metal selected from
Wear. In the wafer prober having such a configuration, the
A silicon wafer with an integrated circuit formed on it
Later, a probe card with tester pins
Pressurize and apply voltage while heating and cooling
Tests can be conducted. Also, such a wafer
Helium leaks from the ceramic substrate that constitutes the prober
The leak amount was 10^-7Pa
・ M^Three / Sec (He) or less, and the ceramic base
The plate is sintered sufficiently densely and this wafer prober
Excellent temperature rise and fall characteristics, withstand voltage and Young's modulus decrease at high temperature
And the wafer prober may be warped.
Absent. When manufacturing a wafer prober, for example,
For example, as in the case of the electrostatic chuck,
The embedded ceramic substrate is manufactured, and then the ceramic
Grooves on the surface of the substrate, and then
Applying sputtering and plating to the surface
A layer may be formed. [0086] The present invention will be described in more detail below. (Examples 1 to 7) Production of electrostatic chuck 101 (see FIG. 3)
Construction (1) Aluminum nitride fired at 500 ° C for 1 hour in air
Powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) 100
0 parts by weight, 40 weights of yttria (average particle size: 0.4 μm)
Parts, 115 parts by weight of acrylic binder, 5 parts by weight of dispersant
And alcohol comprising 1-butanol and ethanol
Using a paste mixed with 530 parts by weight of
Molding by the reed method
Was obtained. (2) Next, the green sheet is heated to 80 ° C.
After drying for 5 hours, the diameter is 1.8m by punching
m, 3.0 mm, 5.0 mm semiconductor wafer support pins
Portion to be inserted through hole, for connecting with external terminal
A portion to be a through hole was provided. (3) Tungsten powder having an average particle diameter of 1 μm
-Bite particles 100 parts by weight, acrylic binder 3.0
Parts by weight, 3.5 parts by weight of α-terpineol solvent and
0.3 parts by weight of powder was mixed to prepare a conductor paste A
Was. 100 weight of tungsten particles having an average particle diameter of 3 μm
Parts, 1.9 parts by weight of acrylic binder, α-terpineo
3.7 parts by weight of dispersant and 0.2 parts by weight of dispersant
Thus, a conductor paste B was prepared. This conductive paste A
Is printed on the green sheet by screen printing,
A strike layer was formed. The printing pattern is a concentric pattern
did. In addition, another green sheet having the shape shown in FIG.
A conductive paste layer composed of an electrostatic electrode pattern was formed. Further, through holes for connecting external terminals are provided.
The conductive paste B was filled in the through hole for the hole. Above
The finished green sheet 50 has additional tongues
Green sheet 50 'without printing ten paste
(Heating surface) 34 sheets, 13 sheets on the lower side are laminated, and then
A grid printed with a conductive paste layer consisting of electrode patterns
Layer 50, and then tungsten
2 green sheets 50 'with no paste printed
Laminate these at 130 ° C., 80 kgf / cm^Two Pressure
To form a laminate (FIG. 8A). (4) Next, the obtained laminated body is
Medium, degreased at 600 ° C for 5 hours, 1890 ° C, shown in Table 1.
Like, pressure 0-200kgf / cm^Two Hot for 3 hours
Press to obtain 3mm thick aluminum nitride plate
Was. This is cut out into a 230 mm disc and the thickness is
6 μm, 10 mm wide resistance heating element 5 and 10 μm thick
Chuck positive electrode electrostatic layer 2 and chuck negative electrode electrostatic layer 3
(FIG. 8B). (5) Next, the plate obtained in (4) is
After polishing with a diamond grindstone, a mask is placed and Si
Bottom hole for thermocouple on the surface by blasting with C etc.
(Diameter: 1.2 mm, depth: 2.0 mm). (6) Further, through holes are formed.
The portions that are present are cut out to form blind holes 35 and 36 (FIG. 8).
(C)) In the blind holes 35, 36, gold made of Ni-Au is used.
Using a wax, heat and reflow at 700 ° C to make Kovar
The external terminals 6 and 18 were connected (FIG. 8D). In addition,
External terminals are connected by a tungsten support at three points
Is desirable. Connection reliability can be ensured
This is because that. (7) Next, a plurality of thermoelectric devices for controlling temperature
Electrostatic chamber having a resistance heating element 5 with a pair embedded in a bottomed hole
Of the hook 101 has been completed. Manufactured in this way
Ceramic of electrostatic chuck 101 having resistance heating element 5
Withstand voltage, thermal conductivity, warpage of substrate (ceramic dielectric film)
Amount, oxygen content, leak amount, fracture toughness value by the following method
Was measured. The results are shown in Table 1 below. (8) Next, this electrostatic chuck 101 is
11 supporting container 41 made of stainless steel having a sectional shape of 11
Ceramic fiber (made by IBIDEN)
) Through a heat insulating material 45. This branch
The holding container 41 has a cooling gas outlet 42 for cooling gas,
The temperature of the electric chuck 101 can be adjusted. this
Resistance of the electrostatic chuck 101 fitted in the support container 41
The heating element 5 is energized to raise the temperature, and
The temperature of the electrostatic chuck 101 was controlled by flowing a coolant through the
However, the temperature could be controlled very well. Embodiment 8 An electrostatic chuck 201 (see FIG. 5)
Production) (1) Aluminum nitride fired at 500 ° C for 1 hour in air
Powder (manufactured by Tokuyama Corporation, average particle size 0.6 μm) 100
0 parts by weight, 40 weights of yttria (average particle size: 0.4 μm)
Parts, 115 parts by weight of acrylic binder, 5 parts by weight of dispersant
And alcohol comprising 1-butanol and ethanol
Using a paste mixed with 530 parts by weight of
Molding by the reed method
Was obtained. (2) Next, the green sheet is heated to 80 ° C.
After drying for 5 hours, the diameter is 1.8m by punching
m, 3.0 mm, 5.0 mm semiconductor wafer support pins
Portion to be inserted through hole, for connecting with external terminal
A portion to be a through hole was provided. (3) A tungsten powder having an average particle diameter of 1 μm
-Bite particles 100 parts by weight, acrylic binder 3.0
Parts by weight, 3.5 parts by weight of α-terpineol solvent and
0.3 parts by weight of powder was mixed to prepare a conductor paste A
Was. 100 weight of tungsten particles having an average particle diameter of 3 μm
Parts, 1.9 parts by weight of acrylic binder, α-terpineo
3.7 parts by weight of dispersant and 0.2 parts by weight of dispersant
Thus, a conductor paste B was prepared. This conductive paste A
Is printed on the green sheet by screen printing.
Conductor paste layer consisting of electrostatic electrode pattern of the shape shown
Was formed. Further, through holes for connecting external terminals are provided.
The conductive paste B was filled in the through hole for the hole. Above
The finished green sheet 50 has additional tongues
Green sheet 50 'without printing ten paste
(Heated surface), and 48 sheets on the lower side.
0 ° C, 80kgf / cm^Two Pressure to form a laminate
Done. (4) Next, the obtained laminated body is
Medium, degreasing at 600 ° C for 5 hours, 1890 ° C, pressure 200
kgf / cm^Two Hot press for 3 hours
An aluminum nitride plate was obtained. This is a 230mm circle
Cut out into a plate shape and hold a 15 μm thick chuck positive electrode
Aluminum nitride having an electric layer 2 and a chuck negative electrode electrostatic layer 3
It was a plate made of aluminum. (5) The bottom surface of the plate obtained in (4) above is
Place the disk and heat the surface by blasting with SiC etc.
A concave portion (not shown) for a thermocouple and the like were provided. (6) Next, the surface facing the wafer mounting surface
The resistance heating element 25 was printed on the (bottom). Printing is conductive page
The strike was used. The conductive paste is
-Sol manufactured by Tokuriki Chemical Laboratory used for forming holes
Best PS603D was used. This conductive paste
Silver / lead paste, lead oxide, zinc oxide, silica, acid
Metal oxides consisting of boron oxide and alumina
The amount ratio is 5/55/10/25/5), and 100 weight of silver
Parts by weight. Also, silver
The shape was scaly with an average particle size of 4.5 μm. (7) Plates printed with conductive paste are
Sinter silver and lead in conductive paste by heating and baking at 80 ° C
And baked on a ceramic substrate. Further sulfur
Nickel acid 30g / l, boric acid 30g / l, ammonium chloride
Contains 30 g / l of sodium and 60 g / l of Rochelle salt
Immerse the plate into an electroless nickel plating bath composed of an aqueous solution
Then, the surface of the silver sintered body 15 was 1 μm thick and contained boron.
A nickel layer 25a having a weight of 1% by weight or less was deposited.
Thereafter, the plate is annealed at 120 ° C. for 3 hours.
Was given. A resistance heating element made of a silver sintered body has a thickness of 5 mm.
μm, a width of 2.4 mm, and a sheet resistivity of 7.7 mΩ /
It was □. (8) Next, a through hole is formed on the ceramic substrate.
A blind hole for exposing the nozzle 16 was provided. N
i-Au alloy (Au 81.5% by weight, Ni 18.4% by weight
%, Impurities 0.1% by weight).
Heat and reflow at 0 ° C to connect external terminal pins made of Kovar.
Continued. Also, solder (tin 9 / lead 1) to the resistance heating element
An external terminal pin made of Kovar was formed through the intermediary. (9) Next, a plurality of thermocouples for temperature control
Was embedded in the concave portion to obtain an electrostatic chuck 201. This
Electrostatic chuck 2 having resistance heating element 5 manufactured as described above
01 ceramic substrate (ceramic dielectric film)
Pressure, thermal conductivity, warpage, oxygen content, leakage, fracture toughness
The property values were measured by the following methods. The results are shown in the table below.
1 is shown. (10) Next, this electrostatic chuck 201 is
Stainless steel support container 41 having the sectional shape of FIG.
Ceramic fiber (made by IBIDEN)
(Wool). this
The support container 41 has a cooling gas outlet 42 for cooling gas,
The temperature of the electrostatic chuck 201 can be adjusted. This
Of the electrostatic chuck 201 fitted in the support container 41
Energize the anti-heating element 15 to raise the temperature and support
The temperature of the electrostatic chuck 201 is controlled by flowing a coolant through the container.
However, the temperature could be controlled very well. (Embodiment 9) Electrostatic chuck 301 (see FIG.
6) Manufacturing (1) Punching 10μm thick tungsten foil
Thus, two electrodes having the shape shown in FIG. 9 were formed. This
Of two electrodes and tungsten wire in air at 500 ° C
Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size: 1.
1 μm) 1000 parts by weight, yttria (average particle diameter: 0.1
4 μm) 40 parts by weight, 115 parts by weight of acrylic binder
In both cases, put them in a mold and press them in nitrogen gas at 1890 ° C and pressure.
Force 200kgf / cm^Two Hot press for 3 hours
A 3 mm aluminum nitride plate was obtained. This is diameter 2
Aluminum nitride plate cut out into a 30mm disk
It was a shape. At this time, the thickness of the electrostatic electrode layer is 10 μm
Met. (2) For this plate-like body,
By performing the steps (5) to (7), the electrostatic chuck 301 is
Obtained. With the resistance heating element 5 manufactured in this manner,
The ceramic substrate of the electric chuck 301 (ceramic dielectric)
Voltage), thermal conductivity, warpage, oxygen content, leak
The amount and fracture toughness value were measured by the following methods. as a result
Are shown in Table 1 below. (Embodiment 10) The electrostatic chuck 401 (see FIG.
7) Manufacturing After performing the steps (1) to (5) of Example 8, furthermore,
Nickel is sprayed on the bottom, and then lead-tellurium-based
By joining the Che elements, the electrostatic chuck 401
Got. It has the resistance heating element 5 manufactured in this way.
Ceramic substrate of the electrostatic chuck 401 (ceramic dielectric
Withstand voltage, thermal conductivity, warpage, oxygen content,
And the fracture toughness value were measured by the following methods. The result
The results are shown in Table 1 below. The static electricity produced in this way
The chuck 401 has excellent temperature-lowering characteristics, and is cooled by a Peltier element.
After cooling, the temperature dropped from 450 ° C to 100 ° C in 3 minutes.
Was. Comparative Example 1 Production of Electrostatic Chuck Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1
μm) 1000 parts by weight, yttria (average particle size: 0.4
μm) 40 parts by weight, acrylic binder 115 parts by weight, min
From 5 parts by weight of powder and 1-butanol and ethanol
Paste containing 530 parts by weight of alcohol
Then, forming by the doctor blade method was performed to obtain a thickness of 0.1 mm.
Same as Example 1 except that a 47 mm green sheet was obtained.
Thus, an electrostatic chuck was manufactured. Made in this way
Ceramic base of electrostatic chuck with fabricated resistive heating element
Withstand voltage, thermal conductivity, warpage of plate (ceramic dielectric film)
Amount, oxygen content, leak amount, fracture toughness value by the following method
Was measured. The results are shown in Table 1 below. Comparative Example 2 Production of Electrostatic Chuck Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size 1.1
μm) 1000 parts by weight, acrylic binder 115 parts by weight
Parts, 5 parts by weight of a dispersant and 1-butanol and ethanol
Containing 530 parts by weight of alcohol consisting of
Using the doctor blade method
Example 1 except that a 0.47 mm green sheet was obtained.
In the same manner as in the above, an electrostatic chuck was manufactured. Like this
Chuck ceramic with resistance heating element
Substrate (ceramic dielectric film) withstand voltage, thermal conductivity,
The following methods are used to determine the amount of leakage, oxygen content, leakage, and fracture toughness.
Was measured by The results are shown in Table 1 below. [0111]Evaluation method (1) Withstand voltage of ceramic substrate (ceramic dielectric film)
Evaluation of Electrostatic chucks manufactured in Examples 1 to 10 and Comparative Examples 1 and 2
The metal electrode on the electrostatic chuck, and
A voltage that applies a voltage between the pole layer and the electrode and causes dielectric breakdown
Was measured. (2) Thermal conductivity a. Used equipment Ligag Laser Flash Method Thermal Constant Measurement System LF / TCM-FA8510B b. Test condition. Temperature: 25 ° C, 450 ° C Atmosphere: vacuum c. Measuring method ・ Temperature detection in specific heat measurement uses silver paste on the back of the sample.
The measurement was performed using a thermocouple (platinel) adhered to the above. ・ At room temperature specific heat measurement, light receiving plate (glassy
Carbon) bonded with silicon grease
The specific heat (Cp) of the sample was calculated according to the following equation (1).
I asked. [0113] (Equation 1) In the above equation (1), ΔOIs the input
The energy, ΔT, is the saturation value of the temperature rise of the sample, Cp
_GC Is the specific heat of glassy carbon, W_GC Is
Sea carbon weight, Cp_SG Of the silicon grease
Specific heat, W_SG Is the weight of silicon grease, W is the sample
Weight. (3) Warpage amount Heat up to 450 ° C and 150kgcm^Two Loaded
Then, cool down to 25 ° C and use a shape measuring instrument (Nano
) Was used to measure the amount of warpage. (4) Oxygen content Trials sintered under the same conditions as the sintered bodies according to the examples and comparative examples
The material is ground in a tungsten mortar and 0.01 g of this is collected.
Sample heating temperature 2200 ° C, heating time 30 seconds 1 condition
Oxygen / nitridation simultaneous analyzer (TC-13 manufactured by LECO)
6). (5) Leak amount Trials sintered under the same conditions as the sintered bodies according to the examples and comparative examples
Fee (area 706.5mm ^Two , Thickness 1mm)
Type helium leak detector (“MSE” manufactured by Shimadzu Corporation)
-11AU / TP type ")
Was measured. (6) Fracture toughness value Vickers hardness tester (MVK-D type manufactured by Akashi Seisakusho)
The indenter is pressed into the surface and the length of the crack
It was measured and calculated using the following formula (2). [0118] Fracture toughness = 0.026 x E^1/2 × 0.5 × P^1/2 × a × C^-3/2... (2) In the above equation (2), E is Young
Rate (3.18 × 10¹¹Pa), P is the indentation load (9
8N), a is half (m) of the average length of the indentation diagonal, C
Is half the average crack length (m). (Embodiment 11) A wafer prober 501 (see FIG.
11) Production (1) Aluminum nitride powder (manufactured by Tokuyama Corporation, average particle size
1.1 μm) 1000 parts by weight, yttria (average particle size:
0.4 μm) 40 parts by weight, acrylic binder 115 parts by weight
Parts, 0.002 parts by weight of boron nitride, 5 parts by weight of a dispersant and
Alcohol 53 comprising 1-butanol and ethanol
Using a paste mixed with 0 parts by weight, doctor blade
Molding by a green method, a 0.47 mm thick green sheet
I got it. (2) Next, the green sheet is heated to 80 ° C.
After drying for 5 hours, heat-generating body and external end by punching
Provided through holes for through holes for connection with slave pins
Was. (3) Tungsten powder having an average particle diameter of 1 μm
-Binder particles 100 parts by weight, acrylic binder 3.0
Parts by weight, 3.5 parts by weight of α-terpineol solvent and dispersion
The conductive paste A was prepared by mixing 0.3 parts by weight of the agent. Ma
100 weight of tungsten particles having an average particle diameter of 3 μm
Parts, 1.9 parts by weight of acrylic binder, α-terpineo
3.7 parts by weight of dispersant and 0.2 parts by weight of dispersant
Thus, a conductive paste B was obtained. Next, the conductive sheet is placed on the green sheet.
Screen printing using strike A, grid-like guard electrode
The printed body for printing and the printed body for ground electrode were printed. Also the end
Conductive through hole for through hole to connect with slave pin
The conductive paste B was filled. Further, a printed green sheet and
50 sheets of unprinted green sheets are stacked and 1
30 ° C, 80kgf / cm^Two With the pressure of
A laminate was produced from the laminate. (4) Next, this laminate is placed in nitrogen gas for 6 hours.
Degreasing at 00 ° C for 5 hours, 1890 ° C, pressure 200kgf
/ Cm^Two Hot-press for 3 hours with a 3 mm thick nitride
A luminium plate was obtained. The obtained plate-like body was treated with a diameter of 30.
Cut out into a 0mm circular shape to make a ceramic plate
Was. The size of the through hole 16 is 0.2 mm in diameter and
It was 0.2 mm. The guard electrode 65 and the ground electrode 66
The thickness of the guard electrode 65 is 10 μm.
1 mm from the mounting surface, the formation position of the ground electrode 66 is
It was 1.2 mm from the wafer mounting surface. In addition, guard electric
Conductor-free area 66a of pole 65 and ground electrode 66
Of one side was 0.5 mm. (5) The plate obtained in the above (4) is
After polishing with a Monde whetstone, place a mask on SiC etc.
Pits and recesses for thermocouples on the surface
Groove 67 for eha suction (width 0.5 mm, depth 0.5 mm)
Was provided. (6) Further, a surface facing the wafer mounting surface
The layer for forming the resistance heating element 61 was printed thereon. printing
Used a conductive paste. The conductive paste is printed
Tokuriki chemistry research used to form through holes in wire
In-house Solvest PS603D was used. This conductive line
The paste is silver / lead paste, lead oxide, zinc oxide,
Metal oxides composed of silica, boron oxide and alumina
The weight ratio of each is 5/55/10/25/5)
It contained 7.5 parts by weight with respect to 100 parts by weight.
In addition, the shape of silver has an average particle size of 4.5 μm and a scale shape.
Met. (7) The heater plate on which the conductive paste is printed is
By heating and firing at 780 ° C, silver and lead in the conductive paste are fired.
And baked on the ceramic substrate 63. Sa
In addition, nickel sulfate 30 g / l, boric acid 30 g / l, chloride
Ammonium 30g / l and Rochelle salt 60g / l
Heater for electroless nickel plating bath consisting of aqueous solution containing
The plate is immersed, and a 1 μm-thick
Nickel layer containing 1% by weight or less of urine (not shown)
Was precipitated. After that, the heater plate is kept at 120 ° C. for 3 hours.
An annealing treatment was performed. Heating element made of sintered silver
Has a thickness of 5 μm, a width of 2.4 mm, and a sheet resistivity of
It was 7.7 mΩ / □. (8) Sputtering is performed on the surface on which the groove 67 is formed.
The titanium layer, molybdenum layer, and nickel
A Kell layer was formed. Equipment for sputtering
SV-4540 manufactured by Vacuum Engineering Co., Ltd. was used. S
The conditions of the puttering were as follows: atmospheric pressure 0.6 Pa, temperature 100 ° C,
Power is 200W and sputtering time is 30 seconds
Adjusted by each metal within a range of 1 minute. Got
The thickness of the film was determined from the image of the fluorescent X-ray analyzer.
0.3 μm, molybdenum layer 2 μm, nickel layer 1 μm
m. (9) Nickel sulfate 30 g / l, boric acid 3
0 g / l, ammonium chloride 30 g / l and roche
Electroless nickel consisting of an aqueous solution containing 60 g / l salt
Immerse the ceramic plate obtained in (8) above in a bath
Thickness on the surface of the metal layer formed by sputtering.
Nickel layer having a thickness of 7 μm and a boron content of 1% by weight or less
Was annealed at 120 ° C. for 3 hours. resistance
The surface of the heating element is covered with electrolytic nickel plating without passing current.
Not overturned. Further, 2 g of potassium potassium cyanide /
l, ammonium chloride 75 g / l, sodium citrate
50 g / l and 10 g / l sodium hypophosphite
Immersed in an electroless gold plating solution at 93 ° C. for 1 minute,
Form a 1μm thick gold plating layer on the nickel plating layer
Was. (10) Air suction from groove 67 to the back
Hole 68 is formed by drilling, and through hole
A blind hole (not shown) for exposing 16 was provided. This
Ni-Au alloy (Au 81.5% by weight, Ni1
8.4% by weight, impurities 0.1% by weight)
Used, heated at 970 ° C and reflowed to make Kovar external end
The child pin was connected. In addition, solder (tin 9
0% by weight / lead 10% by weight)
A child pin was formed. (11) Next, a plurality of thermoelectric
The pair is embedded in the concave portion to obtain a wafer prober heater 501.
Was. Heat the wafer prober with heater to 200 ° C
Then, the temperature was raised to 200 ° C. in about 20 seconds. Also,
The ceramic substrate constituting this wafer prober with heater
Withstand voltage, thermal conductivity, warpage, oxygen content, leak of plate
The amount and the fracture toughness value were measured by the above-described evaluation methods. So
Are shown in Table 1 below. (Example 12) 1 hour in air at 500 ° C
Sintered silicon nitride powder (manufactured by Tokuyama, average particle size 0.6
μm) 100 parts by weight, yttria (average particle size: 0.4 μm)
m) 40 parts by weight, 20 parts by weight of alumina, 40 parts by weight of silica
Parts, acrylic binder 11.5 parts by weight, dispersant 0.5 weight
Parts, and 1-butanol and ethanol
Use a paste mixed with 53 parts by weight of alcohol,
Formed by tar blade method, thickness 0.50mm
Green sheet was obtained. Using this green sheet
The firing conditions were as follows: temperature 1900 ° C, pressure 200 kgf / c
m^Two Except that the steps (2) to (8) of Example 1
Similarly, an electrostatic chuck was manufactured. Obtained electrostatic tea
Voltage, warpage, oxygen content,
Leak amount and fracture toughness were measured by the above evaluation methods.
Was. The results are shown in Table 1 below. (Comparative Example 3) The amount of yttria was 0.2 weight
Except that the electrostatic chuck was used in the same manner as in Example 7.
Manufactured. Resistance of the ceramic substrate of the obtained electrostatic chuck
Voltage, thermal conductivity, warpage, oxygen content, leak amount, breakdown
The toughness value was measured by the evaluation method described above. The result
The results are shown in Table 1 below. Comparative Example 4 The firing temperature was 1600 ° C.
Except that no pressing was performed, the electrostatic
A chuck was manufactured. Ceramics of the obtained electrostatic chuck
Voltage, thermal conductivity, warpage, oxygen content, leakage
And the fracture toughness value were measured by the above-described evaluation methods.
The results are shown in Table 1 below. (Example 13) 300 kgf / cm^Two Add
The electrostatic chuck was operated in the same manner as in Example 1 except that pressure was applied.
Was manufactured. The obtained electrostatic chuck ceramic substrate
Withstand voltage, thermal conductivity, warpage, oxygen content, leak amount, breakage
The fracture toughness value was measured by the evaluation method described above. as a result
Are shown in Table 1 below. [0139] [Table 1] As is clear from the results shown in Table 1, the actual
Ceramic constituting electrostatic chucks according to Examples 1 to 13
On the substrate, a helium leak detector measured with a helium leak detector was used.
The leak amount of all^-7Pa ・ m^Three / Sec or less
Therefore, their withstand voltage shows a large value,
The characteristics are good and the amount of warpage is a small value. On the other hand, the ratio
The ceramic substrate constituting the electrostatic chucks of Comparative Examples 1 to 4
Indicates that the leak amount of helium is 10^-7Pa ・ m^Three
/ Sec, these withstand voltages are quite small.
The temperature rise and fall characteristics are poor, and the amount of warpage is large.
All the results were inferior to Examples 1 to 13.
Indicates the value. As described above, the ceramic substrate of the present invention
Is 10 measured by a helium leak detector.^-7Pa
・ M^Three / Sec (He)
The amount of decrease in thermal conductivity at high temperatures is small.
No. Also, the withstand voltage at high temperature is high. Also, the amount of warpage is small
No. Also, if the leak amount is 10^-13 Pa ・ m^Three / Sec (H
In the case of e), on the contrary, the amount of decrease in thermal conductivity becomes large,
In addition, the fracture toughness value also decreases. The reason is not clear
However, if the densification proceeds too much, oxygen
Diffuses into the crystal, lowering the crystallinity,
The cracks are easier to extend
Estimated. [0142] As described above, the ceramic of the present invention
The substrate was measured with a helium leak detector and measured at 10
^-7Pa ・ m^Three / Sec (He) or less
It has excellent temperature rise / fall characteristics and high temperature resistance
The voltage is large and the amount of warpage is small.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a plan view schematically showing an example of a ceramic heater using a ceramic substrate of the present invention. FIG. 2 is a partially enlarged cross-sectional view of the ceramic heater shown in FIG. FIG. 3 is a cross-sectional view schematically showing one example of an electrostatic chuck using the ceramic substrate of the present invention. 4 is a cross-sectional view of the electrostatic chuck shown in FIG. FIG. 5 is a cross-sectional view schematically showing one example of an electrostatic chuck using the ceramic substrate of the present invention. FIG. 6 is a cross-sectional view schematically showing one example of an electrostatic chuck using the ceramic substrate of the present invention. FIG. 7 is a cross-sectional view schematically showing one example of an electrostatic chuck using the ceramic substrate of the present invention. FIGS. 8A to 8D are cross-sectional views schematically showing a part of the manufacturing process of the electrostatic chuck shown in FIG. FIG. 9 is a horizontal sectional view schematically showing a shape of an electrostatic electrode constituting the electrostatic chuck according to the present invention. FIG. 10 is a horizontal sectional view schematically showing the shape of an electrostatic electrode constituting the electrostatic chuck according to the present invention. FIG. 11 is a cross-sectional view schematically showing a state where the electrostatic chuck according to the present invention is fitted into a support container. FIG. 12 is a cross-sectional view schematically showing a wafer prober using the ceramic substrate of the present invention. 13 is a cross-sectional view schematically showing a guard electrode of the wafer prober shown in FIG. DESCRIPTION OF SYMBOLS 101, 201, 301, 401 Electrostatic chuck 1 Ceramic substrate 2, 22, 32a, 32b Chuck positive electrode electrostatic layers 3, 23, 33a, 33b Chuck negative electrode electrostatic layers 2a, 3a Semicircular portion 2b , 3b comb tooth part 4 ceramic dielectric film 5, 12 resistance heating element 6, 13, 18 external terminal 7 metal wire 8 Peltier element 9 silicon wafer 11 ceramic substrate 14 bottomed hole 15 through hole 19 through hole 26 support pin

   ────────────────────────────────────────────────── ─── Continuation of front page    F term (reference) 3K092 PP20 QA05 QB02 QB03 QB43                       RF03 RF11 RF17 RF27 SS12                       SS34 VV40                 4G030 AA01 AA02 AA03 AA04 AA07                       AA12 AA16 AA17 AA32 AA35                       AA36 AA37 AA40 AA45 AA47                       AA49 AA50 AA51 AA52 AA60                       AA61 BA12 BA20 BA21 BA23                       CA07 CA08 GA11 GA19 GA24                       GA27 GA29 GA35                 5F031 CA02 HA02 HA16 HA33 HA37                       MA28 MA32 PA13 PA30

Claims (1)

[Claims] 1. A conductive material on the surface or inside of a ceramic substrate
A ceramic substrate on which a body is formed;
Mic substrate is measured by helium leak detector.
10^-7Pa ・ m ^Three / Sec (He) or less
Ceramic substrate.