JP5544678B2 - Processing system and processing method of object to be processed - Google Patents

Description

  The present invention relates to a processing system using an extremely low moisture gas for reducing moisture from the surface of a thin film to the limit, and a method for processing an object to be processed using the extremely low moisture gas.

  In recent years, development of technology for dehydrating and removing water from a solid surface of a metal, an insulator, a semiconductor, or the like, or from the inside of the solid has progressed. Especially in the manufacture of semiconductors, electrical / electronic components, etc., not only dehydration from the equipment wall surface metal of the manufacturing equipment, but also adhered to the deposited thin film, especially the surface of the metal, insulator / semiconductor thin film, organic EL layer, liquid crystal, etc. It is essential to dehydrate and remove moisture. This is because residual moisture greatly affects the reliability of thin films, and hence the reliability of semiconductors and electrical / electronic component devices. Therefore, it is necessary to sufficiently reduce the amount of moisture when manufacturing semiconductors and electrical / electronic components. Because there is.

  Therefore, dehydration in the production environment is essential, but in normal air at room temperature, dehydration drying from the surface takes a long time, so dehydration drying under a vacuum reduced from atmospheric pressure is required. Widely done. This is based on the effect of lowering the partial pressure of water vapor and promoting evaporation by setting the pressure lower than usual. Furthermore, the member and the film are heated to about 100-200 ° C. under the above-mentioned vacuum to promote the evaporation of water more actively, and the dehydration process is performed in a shorter time.

  For example, in semiconductor and electrical / electronic component manufacturing equipment, to evacuate the equipment from atmospheric pressure and achieve a high-quality vacuum without water, the equipment is heated to 100 ° C-200 ° C under vacuum, and stainless steel is used. Alternatively, a technique is used in which moisture adhering to the inner wall portion of the apparatus made of aluminum or the like is removed by heating, and the degree of vacuum reached is improved. Also, in the manufacture of semiconductors and electrical / electronic component devices, residual moisture contained in semiconductor thin films is reduced as much as possible by performing thin film deposition, heat treatment, and etching processes in devices that have sufficiently improved ultimate vacuum. This reduces the deterioration of the film due to moisture, oxidation, and deterioration of reliability. In addition, after the thin film is deposited, water is usually removed from the thin film. Furthermore, various components constituting the semiconductor and electrical / electronic component manufacturing apparatus are incorporated in the apparatus after sufficient dehydration treatment by performing heat dehydration treatment in a vacuum chamber in advance.

As described above, conventionally, in order to dehydrate and remove moisture from a solid surface such as a metal, an insulator, or a semiconductor and from the inside of the solid, the material / member is usually heated in a vacuum apparatus. However, since resin parts and the like are included, there is a heat resistance limit inherent to vacuum device materials, and there is a restriction that, for example, sufficient dehydration cannot be performed because heating is normally limited to 100-200 ° C. In addition, since heating in a low vacuum of about 10 ^-5 Pa is usually used at the maximum, dehydration is not performed under a sufficiently low water pressure, and therefore it is affected by residual moisture. was there. In particular, in the prior art, it has been generally difficult to reduce the amount of water in a vacuum apparatus or a dry gas to 1 PPB or less even when a dehydration treatment in a gas is performed using an adsorbent or the like. Therefore, in the present invention, an atmosphere dried to the limit where the amount of moisture in the gas is 1 PPB or less is realized by using a novel technique, and dehydration treatment and manufacturing of semiconductors and electrical / electronic component devices are performed using the atmosphere. Providing a new environment to perform is an issue.

  On the other hand, in the manufacture of semiconductors and electrical / electronic components, it is necessary to remove moisture to the limit, particularly when depositing thin films and introducing raw materials, but until now it has been impossible to reduce the amount of moisture as an impurity to 1 PPB or less. Therefore, there is a problem that residual moisture exists in the film and the maintenance cycle of the apparatus is lowered. Therefore, in the present invention, a second problem is to realize an environment in which a moisture content is dried to 1 PPB or less and to realize an environment in which semiconductors and electrical / electronic parts are manufactured.

  Generally used gas for industrial use such as inert gas and nitrogen contains oxygen as an impurity although it is a trace amount. This can be a problem for oxygen molecules when there is a process aimed at preventing oxidation in all fields. For example, there may be a problem in the production of a metal thin film by CVD, sputtering, etc., in the production of an intermetallic compound, or in the wiring process of a semiconductor or electrical / electronic component manufacturing process.

(1) The processing system of the present invention
A pair of metal tubes;
A ceramic solid electrolyte body connected to each of the tubes and having a hollow through which gas from the tubes passes;
An inner electrode and an outer electrode provided on the inner surface of the electrolyte body;
Here, the tube body is made of a metal material that is substantially the same as the thermal expansion coefficient of the ceramic material that constitutes the inner electrode together with the inner electrode, and is hermetically fixed to the solid electrolyte body,
An oxygen molecule discharging apparatus comprising:
A heating device for heating the oxygen molecule discharging device;
Applying means for applying a voltage between the electrodes of the oxygen molecule discharging apparatus;
Here, an oxygen partial pressure control device that controls the partial pressure of oxygen in the gas passing through the hollow by applying voltage between the electrodes of the oxygen molecule discharging device by turning on voltage application during the oxygen molecule discharging is provided. An extremely low moisture gas generating device for generating a moisture content in the gas to 1 PPB or less;
And a processing apparatus in which an extremely low moisture gas having an amount of moisture of 1 PPB or less introduced into the gas generated by the extremely low moisture gas generating apparatus is introduced and the moisture inside the apparatus is removed.

(2) The processing system of the present invention
A pair of metal tubes;
A ceramic solid electrolyte body connected to each of the tubes and having a hollow through which gas from the tubes passes;
An inner electrode and an outer electrode made of gold or platinum provided on the inner surface of the electrolyte body;
The tubular body is made of a Kovar material having substantially the same thermal expansion coefficient as that of the solid electrolyte body made of zirconia, and is fixed to the solid electrolyte body by silver brazing, and the tubular body has an inner side together with the platinum inner electrode. Configure the electrodes,
An oxygen molecule discharging device comprising:
A heating device for heating the oxygen molecule discharging device;
Applying means for applying a voltage between the electrodes of the oxygen molecule discharging apparatus;
Turning on the voltage application when the oxygen molecules are discharged;
An oxygen partial pressure control device that controls a partial pressure of oxygen in a gas passing through a hollow by applying a voltage between electrodes of the oxygen molecule discharging device, and generates an extremely low water content in the gas to 1 PPB or less. A moisture gas generator;
A processing apparatus in which an extremely low moisture gas having a moisture content of 1 PPB or less introduced in the gas generated by the extremely low moisture gas generation apparatus is introduced, and moisture is dehydrated and removed from an object to be processed provided in the apparatus; Comprising.

(3) The processing system of the present invention
A pair of metal tubes;
A ceramic solid electrolyte body connected to each of the tubes and having a hollow through which gas from the tubes passes;
An inner electrode and an outer electrode made of gold or platinum provided on the inner surface of the electrolyte body;
The tubular body is made of a Kovar material having substantially the same thermal expansion coefficient as that of the solid electrolyte body made of zirconia, and is secured to the solid electrolyte body by silver brazing, and the silver brazing secured portion and the tubular body are: An electroplating layer electroplated with gold or platinum, and an electroless plating layer electrolessly plated with gold or platinum after pretreatment of the electroplated portion with acid or alkali,
An oxygen molecule discharging device comprising:
A heating device for heating the oxygen molecule discharging device;
And an oxygen partial pressure control device for controlling the oxygen partial pressure in the gas passing through the hollow by applying a voltage between the electrodes of the oxygen molecule discharging device, and generating an extremely low moisture content in the gas of 1 PPB or less. A gas generator;
A processing apparatus into which an extremely low moisture gas having a moisture content of 1 PPB or less generated in the gas generated by the extremely low moisture gas generating apparatus is introduced, and the gas is an etching gas for an object to be processed and a sputtering gas Or any one of the carrier gases;
A processing system comprising:

(4) In the processing system of (2),
The object to be processed is any one of a stainless plate, an aluminum plate, an alumina plate, a glass plate, a quartz plate, a silicon wafer, an insulating film, a metal film, or a semiconductor film deposit.

(5) In any of the processing systems (1) to (3),
The oxygen partial pressure in the gas is 10 minus 21 squared or less, preferably 10 minus 29 squared or less, 10 minus 35 squared or more.

(6) In any of the processing systems (1) to (3),
Further, the vacuum evacuation and the purge by introducing an extremely low moisture gas having a moisture content of 1 PPB or less are repeated.

(7) Using the processing system according to any one of (1) to (3), processing the object to be processed for dehydrating and removing the water from the object to be processed in an atmosphere in which the amount of water in the gas is controlled to 1 PPB or less. It was a method.

(8) A processing method of an object to be processed for etching the object to be processed in an atmosphere in which the amount of moisture in the gas is controlled to 1 PPB or less using the processing system of (1) or (2).

(9) Using the processing system of (1) or (2), a processing method of an object to be processed for depositing a thin film on a substrate in an atmosphere in which the amount of moisture in the gas is controlled to 1 PPB or less.

(10) A processing method for an object to be processed for heat-treating the object to be processed in an atmosphere in which the moisture content in the gas is controlled to 1 PPB or less using the processing system of (1) or (2) did.

(11) A processing method of an object to be processed for processing an object to be processed using a gas whose water content is controlled to 1 PPB or less as a raw material carrier gas using the processing system of (1) or (2) It was.

  According to the present invention, dehydration can be performed in an environment where the moisture content is 1 PPB or less, which has not been realized so far. Thereby, the remarkable effect which shortens dehydration time remarkably and reduces a residual water | moisture content is acquired. In addition, since semiconductors and electrical / electronic component devices can be manufactured in an environment with very little water, water remaining as impurities in the semiconductors and electrical / electronic component devices can be reduced to the limit.

  Embodiments of the present invention will be described below with reference to the drawings.

  FIG. 1 shows a schematic diagram of a processing system according to the present invention. The processing system 10 includes a processing device 12, a vacuum pump 14 for depressurizing the inside of the vacuum processing container 12, and extremely low moisture gas generation for supplying an extremely low moisture gas having a moisture content of 1 PPB or less into the vacuum processing device 12. Device 16. Reference numeral 18 denotes a sample provided in the vacuum processing apparatus 12.

FIG. 2 shows a schematic diagram of a semiconductor or electrical / electronic component manufacturing apparatus as a vacuum processing apparatus. The semiconductor manufacturing apparatus 12 includes a load lock 22 and a vacuum processing chamber 12. The load lock chamber 22 is evacuated to 1 × 10 ⁻⁴ Pa, and the vacuum processing vessel 12 is evacuated to 1 × 10 ⁻⁵ Pa. The vacuum processing vessel 12 is provided with a plasma source 24 and a heater 26, and a thin film is deposited and etched. Further, the semiconductor manufacturing apparatus is provided with an extremely low moisture gas generating device 16 including an electrochemical oxygen molecule discharging device that discharges moisture from the source gas 28. The semiconductor manufacturing apparatus heats the wafer 25 or deposits a thin film in an inert gas of ultra-low moisture having a water content of 1 PPB or less and an oxygen partial pressure of 10 ⁻³⁵ atm from the raw material cylinder 30.

FIG. 3 is a main part schematic diagram showing an oxygen molecule discharging apparatus 20 constituting the extremely low moisture gas generating apparatus of FIGS. 1 and 2. The oxygen molecule discharging apparatus 20 includes a zirconia solid electrolyte body 40 having oxygen ion conductivity, and net-like electrodes 42 and 44 made of gold or platinum disposed on the inner and outer surfaces of the solid electrolyte body 40. The zirconia solid electrolyte body 40 is fixed at both ends by a metal tube 46 made of a copal material and a silver brazing 48. The electrode of the solid electrolyte body and the tube body 46 constitute an inner electrode. The internal pressure of the oxygen molecule discharging apparatus is 3 kg / cm ² or less, is usually 0.1~1.0kg / cm ^2.

FIG. 4 is a schematic diagram showing the operation of the oxygen molecule discharging apparatus 20. When a current I is passed from the DC power source E between the inner surface electrode 42 and the outer surface electrode 44, water molecules (H ₂ O) present in the sealed container are electrolyzed into hydrogen ions and oxygen ions by the inner surface electrode 42, and the solid electrolyte After passing through 40, oxygen molecules (O ₂ ) are released again outside the sealed container. Therefore, the oxygen molecules released outside the sealed container are sealed by exhausting auxiliary gas such as air as a carrier gas. The amount of water can be reduced by removing water molecules in the inert gas supplied to the container. Subsequently, the oxygen molecules released to the outside of the sealed container are exhausted using an auxiliary gas such as air as a carrier gas to remove oxygen molecules in the inert gas supplied to the sealed container, and the oxygen content is reduced. The pressure can be controlled simultaneously.

  As described above, the oxygen molecule discharging apparatus discharges oxygen molecules in the gas to the outside air while the gas introduced into the solid electrolyte body 40 passes through the solid electrolyte body 21 to generate extremely low moisture gas, Supply from the solid electrolyte body toward the vacuum processing apparatus. In FIG. 4, ● is a gas, OO is a water molecule and an oxygen molecule, and ◯ is a water ion and an oxygen ion.

Next, the operation of the extremely low moisture gas generator will be described. First, a desired moisture amount, for example, 1 PPT is set by the moisture amount setting unit. A control signal for setting the moisture amount set by the moisture amount setting unit is sent from the moisture pressure control unit to the pump. The current I of the pump is controlled by the control signal, and the amount of water in the inert gas such as N ₂ , Ar, and He supplied to the oxygen molecule discharging device through the gas supply valve and the mass flow controller is set to the amount of water. The amount of water set by the unit is controlled.

  The inert gas controlled to have a very low moisture content is supplied to the reaction chamber of the vacuum processing apparatus after its partial pressure is monitored by the moisture sensor. Further, the moisture pressure of the used gas exhausted through the vacuum reaction chamber is monitored by the moisture sensor, and the monitored value is input to the moisture amount control unit, and is compared with the set value by the moisture amount setting unit. In this way, an inert gas whose water content is controlled to 1 PPT or less is supplied. The pressure during the treatment may be performed under reduced pressure, or from normal pressure to increased pressure, and the used gas may be exhausted outside the apparatus via a vacuum pump, or the treatment may be performed. In the meantime, a closed loop may be formed so that the spent gas is returned to the oxygen molecular gas discharge device again. The water content can be obtained from thermodynamic calculation using an oxygen sensor using an oxygen ion conductor.

The solid electrolyte constituting the solid electrolyte body 40 is, for example, a general formula (ZrO ₂ ) 1-xy (In ₂ O ₃ ) x (Y ₂ O ₃ ) y (0 <x <0.20, 0 <y <020, 0.08). A zirconia system represented by <x + y <0.20) can be used. Among them, 0 <x <0.20 and y = 0 are preferable, and 0.06 <x <0.12 and y = 0 are more preferable.

In addition to those exemplified above, the solid electrolyte is, for example, a composite B oxide containing Ba and In, in which a part of Ba of the composite oxide is replaced by solid solution with La, in particular, the atomic ratio {La / (Ba + La) } what was 0.3 or more and, and those further substituted for part of in in Ga, formula {Ln 1 - x Srx Ga 1 - (y + z) Mg y Co z O 3 However, one or two of Ln = La and Nd, x = 0.05 to 0.3, y = 0 to 0.29, z = 0.01 to 0.3, y + z = 0.025 to 0.3}, or a general formula {Ln ( 1-x) AxGa (1-y-z) B1yB2zO3-d, provided that Ln = La, Ce, Pr, Nd, Sm or one or more of A, S = Sr, Ca, Ba One or more species, B 1 = Mg, Al, In, B 2 = Co, Fe, Ni, Cu 1 type or 2 types or more, or a general formula {Ln2-xMxGe1-yLyO5, where Ln = La, Ce, Pr, Sm, Nd, Gd, Yd, Y, Sc, M = One or more of Li, Na, K, Rb, Ca, Sr, Ba, L = one or more of Mg, Al, Ga, In, Mn, Cr, Cu, Zn} Formula {La (1-x) SrxGa (1-y-z) MgyAl2O3, where 0 <x≤0.2, 0 <y≤0.2, 0 <z <0.4} and the general formula {La (1 -x) A x Ga (1 -y-z) B 1y B 2z O 3, provided that Ln = La, Ce, Pr, Sm, Nd, one or more, A = Sr, Ca, Ba 1 type or 2 types or more, B 1 = 1 type or 2 types or more of Mg, Al, In, B 2 = 1 type or 2 types or more of Co, Fe, Ni, Cu , X = 0.05~ 0.3, y = 0~ 0.29, z = 0.01~ 0.3, y + z = 0.025~ 0.3} and the like can be employed.

  The good airtightness between the both ends of the solid electrolyte body and the pipe body described above has a strong influence on moisture and oxygen partial pressure. In order to exhibit ionic conductivity, the solid electrolyte is heated to 600 ° C to 1000 ° C. When reducing the moisture content of the extremely low moisture gas, it is preferable to heat the solid electrolyte to a higher temperature. Conventionally, both ends are kept airtight using an O-ring or an adhesive for vacuum equipment, but measures such as air cooling have been taken in consideration of heat resistance. However, sufficient confidentiality could not be obtained. As a sealing structure between both ends of the solid electrolyte body and the tube body, it is adopted to join the tube body and the solid electrolyte body with metal brazing. As a result, the heat-resistant temperature is improved, so that high airtightness can be obtained and a lower extremely low moisture gas can be obtained.

  Further, considering the heat resistance of the seal structure and the improvement of the function of the oxygen molecule discharging device, it is desirable that there are a plurality of solid electrolyte bodies constituting this oxygen molecule discharging device, and each solid electrolyte body is The longer it is, the better the molecule discharging function, and the sealing function can be provided at a distance from the heating part. Therefore, it is not necessary to consider the heat resistance of the tubular body. However, the solid electrolyte body preferably has a length of 15 cm to 60 cm in consideration of cost and handling. The length of each tube on one side is desirably 3 cm to 60 cm.

  The sealing structure for maintaining the sealing between the both ends of the solid electrolyte body and the tube body was performed as follows. Both ends of the solid electrolyte body and the tube are fixed by silver brazing. Next, the silver brazing fixing portion and the metal tube are subjected to electrolytic plating with gold or platinum. Then, after the electrolytic plating portion is pretreated with acid or alkali, the solid electrolyte body is also subjected to electroless platinum plating.

  As shown in FIGS. 5 and 6, six zirconia tubes doped with 6% mol of yttria having a length of 50 cm 2 were used as the solid electrolyte body. The airtightness between the tube body 46 and the zirconia tube 40 was improved by strength and heat resistance by bonding by silver brazing. Six zirconia tubes 40 were arranged in parallel in the container 50. Heater heaters 52 are disposed above and below the zirconia tube.

  Argon gas was introduced from the gas inlet, and the mass flow controller was set to 2 L / min. The zirconia tube was heated to 600 ° C. to 1000 ° C., and 2 V was applied as a voltage between both electrodes on the inner and outer walls. It should be noted that air is allowed to flow as a purge gas outside the solid electrolyte body.

  Subsequently, water that passed through the zirconia tube in the molecular discharger and gas with reduced oxygen partial pressure were introduced to a water / oxygen sensor, and the oxygen partial pressure was measured. The oxygen partial pressure was measured by using an electromotive force generated by a concentration cell reaction associated with a difference in oxygen partial pressure inside and outside the solid electrolyte body. At this time, in about 2 hours, the oxygen partial pressure showed 10 minus 21 squared atmospheric pressure, preferably 10 minus 29 squared atmospheric pressure to 10 minus 35 squared atmospheric pressure.

An extremely low moisture gas was introduced into the semiconductor manufacturing apparatus, and the moisture in the processing container was removed as follows. First, the inside of the container is evacuated to about 10 ⁻⁵ Pa by a turbo molecular pump, and then nitrogen gas having an oxygen partial pressure of −35 and a moisture content of 1 PPT or less is introduced at a flow rate of 2 SLM, so that atmospheric pressure or pressurization is achieved. The container was filled to the state. Subsequently, the introduction of nitrogen gas was stopped, and the operation of evacuating to 10 ⁻⁵ PaPa again with a turbo molecular pump and further flowing the nitrogen gas to atmospheric pressure was repeated. Thereafter, the above operation was repeated a total of 6 times, and then the vacuum vessel was again evacuated by a vacuum pump.

  FIG. 7 shows an exhaust curve from atmospheric pressure at that time. It was found that both the exhaust speed and the ultimate vacuum after the introduction of the extremely low moisture gas were improved as compared with the case where only the vacuum evacuation was performed without removing the moisture with the extremely low moisture gas. Therefore, when the moisture in the apparatus was examined, it was found that when the extremely low moisture gas according to the present invention was introduced, the moisture content inside the vacuum processing vessel was reduced, and the exhaust speed and ultimate vacuum were improved. The moisture reduction effect is effective if a low moisture gas is introduced into the container at least once. Further, as the kind of gas, in addition to nitrogen, which is a general inert gas, argon, helium It was confirmed that the use of an inert gas such as.

In addition, when an extremely low moisture gas is heated to 100 ° C.-200 and introduced into a vacuum processing container, the vacuum processing container is further heated (baked) to 100 ° C. and an extremely low moisture gas is introduced. As a result, it was found that moisture was more efficiently removed and the ultimate vacuum was further improved.
Furthermore, the vacuum processing vessel, when sprayed with extremely low moisture gas jet pressurized to about 0.1 ^-1 Mpa at a high speed, by spraying effect, moisture is effectively removed in a shorter time I understood that.
In addition, when nitrogen gas is continuously flowed into the vacuum processing vessel without using a repetitive operation of nitrogen gas and evacuation, so-called cycle purge, the same effect of improving the ultimate vacuum can be obtained. I understood that. In this case, excess nitrogen gas leaks from the vacuum processing container when the pressure exceeds atmospheric pressure, but the leaked gas may be exhausted and discharged as it is, or the overflow gas is returned to the extremely low moisture generator again. It was found that the same effect was obtained when a kind of closed loop was constructed in which the amount of water was reduced again and returned to the container.

  The material of the semiconductor manufacturing apparatus may be made of stainless steel (SUS304, 316, 316L), aluminum, or quartz. Furthermore, the semiconductor manufacturing apparatus includes various devices such as a wafer heating mechanism, a plasma source, and a wafer support mechanism. Even if there is an incidental mechanism, the same effect can be obtained.

  Dehydration treatment from 6 inch diameter SUS plate, aluminum plate, anodized aluminum plate, alumina plate, glass plate, quartz plate, silicon wafer, plastic substrate and organic film, introduces extremely low moisture gas It went as follows.

First, the various members were washed with ultrapure water and then placed in a vacuum processing container for processing. First, the inside of the vacuum processing vessel was evacuated to about 10 ⁻⁵ Pa by a turbo molecular pump, and then nitrogen gas having an oxygen partial pressure of 10 ^{−35 to} atmospheric pressure and a water content of 1 PPT or less was introduced at a flow rate of 2 SLM. The introduction may be performed under vacuum, atmospheric pressure, or a pressurized state. Subsequently, the introduction of nitrogen gas was stopped, and the operation of evacuating again to 10 ⁻⁵ Pa with a turbo molecular pump and flowing the nitrogen gas to atmospheric pressure was repeated. Thereafter, the above operation was repeated a total of 6 times, and then the vacuum processing container was again evacuated by a vacuum pump.
As a result, it was found that both the exhaust speed and the ultimate vacuum after the introduction of this gas were improved as compared with the case where only the vacuum evacuation was performed without removing the moisture with the extremely low moisture gas. That is, it was found that dehydration and drying can be performed effectively.

Note that the effect of reducing moisture is effective if a low moisture gas is introduced into the apparatus at least once in the apparatus under reduced pressure. Furthermore, the type of gas is a general inert gas. It was confirmed that the use of an inert gas such as argon or helium other than nitrogen would have the same effect. In addition, when the low oxygen gas is heated to 100 ° C.-200 ° C. and introduced into the container, and further, the inside of the container is heated (baked) to 200 ° C. with a heater and the low moisture gas is introduced, the exhaust rate is increased. It was also found that the ultimate vacuum was further improved. Furthermore, the vacuum vessel, when sprayed with extremely low moisture gas jet pressurized to about 0.1 ^-1 Mpa at a high speed, by spraying effect, the shorter time the water is efficiently removed I understood.
In addition, when nitrogen gas is continuously flowed into the drying apparatus without performing a repetitive operation of nitrogen gas and evacuation, so-called cycle purge, the same effect of improving the ultimate vacuum can be obtained. I understood that. In this case, excess nitrogen gas leaks from the drying device when the atmospheric pressure is exceeded, but this leaked gas may be exhausted and discharged as it is, or the gas is returned to the extremely low moisture gas generator again, It has been found that the same effect can be obtained when a kind of closed loop is constructed in which the amount of slag is reduced again and returned to the manufacturing apparatus. In addition, it cannot be overemphasized that this effect is effective in spin-drying | dehydrating not only the various board | plate described above but all members.

In the semiconductor device, the dehydration process from the inside of the thin film and from the surface thereof was performed with an extremely low moisture gas as follows. The gas was used for dehydration treatment from the insulating film. Heat treatment at 300 ° C. was performed with a heat treatment apparatus using a wafer in which a silicon oxide film was deposited to a thickness of 100 nm on a silicon wafer. When a gas having a water content of 1 PPT or less and an oxygen partial pressure of 10 ^{−35 to the} atmospheric pressure is introduced into the heat treatment apparatus at a flow rate of 2 SLM and the substrate is heated to 300 ° C., the effect of significantly reducing the moisture remaining in the silicon oxide film and on the surface was gotten. Subsequently, when a dehydration process was performed in the same manner using a wafer in which a carbon-containing silicon oxide film having a relative dielectric constant of 3.0 was deposited on a silicon wafer to a thickness of 100 nm, a remarkable decrease in moisture in the film and on the film surface was also observed. It was. Similarly, when a metal film such as aluminum or copper, or a semiconductor film such as silicon or germanium was heat-treated, the same effect of remarkably reducing the moisture on the surface was obtained. In addition, when the low oxygen gas is heated to 100 ° C.-200 ° C. and introduced into the apparatus, and further, an extremely low moisture gas jet pressurized to about 0.1 ⁻¹ Mpa is sprayed at a high speed, It was found that moisture was efficiently removed in a shorter time.

An example in which an extremely low moisture gas was applied to the deposition of a thin film in a semiconductor or electrical / electronic component device was performed as follows. In the deposition of polysilicon, first, monosilane gas is introduced into the vacuum reaction chamber at a flow rate of 100 sccm, and at the same time, nitrogen gas having a water content of 1 PPT or less and an oxygen partial pressure of 10 ^{−35 to the} atmospheric pressure is introduced at a flow rate of 500 sccm. A polysilicon film was deposited on the silicon substrate at ⁻¹ P and a substrate temperature of 600 ° C. As a result, the effect of significantly reducing the amount of moisture and oxygen in the polysilicon film was obtained. Although decomposition of monosilane by heat is used, decomposition using plasma at a lower temperature may be used. Of course, it is needless to say that the present invention can be applied to the production of thin films other than the deposition of a polysilicon film.

  Sputtering was performed with extremely low moisture gas as follows. Introduced into the apparatus at a rate of 1 scpt or less and a 10-35 oxygen partial pressure of oxygen in argon gas at 100 sccm, turned into plasma at a pressure of 1 Pa and a power of 200 W, and collided with an aluminum plate as a target to form silicon by sputtering. When an aluminum thin film was deposited on the substrate, low-resistance aluminum having a low oxygen concentration in the film was formed.

Plasma etching of the thin film was performed with an extremely low moisture gas as follows. A CF4 gas having a water content of 1 PPT or less and an oxygen partial pressure of 10 ^{−35 to the} atmospheric pressure is introduced into the apparatus at 100 sccm, converted into plasma at a pressure of 1 Pa and power of 200 W, and sprayed onto a silicon oxide substrate. The fine pattern formed on the silicon oxide film can be uniformly etched without any shape abnormality.

An example in which an extremely low moisture gas was applied as a raw material carrier gas for thin film deposition was performed as follows. As raw materials, it was applied to chlorides, organic metals, TiCl ₄ , Ti [N (CH ₃ ) ₂ ] ₄ , HfCl ₄ , Hf [N (CH ₃ ) ₂ ] ₄ . These raw materials were charged into a source cylinder to heat the cylinder to 50-100 ° C., allowed to further flow into the water content 1PPT less and an oxygen partial pressure of 10 ^-35 square extremely low moisture nitrogen gas pressure at a flow rate of 100 sccm, a raw material chlorides In addition, a mixture of vaporized and organic metal vaporized in an extremely low moisture gas was introduced into the vacuum processing chamber. Further, when the silicon wafer was heated to about 300 ° C., a metal film such as titanium or hafnium was deposited on the wafer depending on the raw material used. Since the extremely low moisture gas was used, the moisture in the piping was remarkably reduced, and as a result, a remarkable reduction effect was obtained in the number of particles generated from the riding pressure cylinder. In particular, the effect of extending the life of the source gas line by several times was obtained. Moreover, the effect of reducing the water content and the residual oxygen content in the deposited film was obtained as compared with the conventional one using an inert gas.
In addition, this extremely low moisture gas is also effective for producing display electronic devices such as liquid crystals and organic EL elements. That is, the liquid crystal of the encapsulation process or during deposition of the organic EL light-emitting layer, the moisture content 1PPT less and an oxygen partial pressure of 10 ^-35 square extremely low moisture nitrogen gas pressure is flowed in 2SLM from the flow 100 sccm, a sufficient water By removing it, a highly reliable display electronic device can be manufactured.

  It is used in the field of manufacturing products using extremely low moisture gas, and can be used for semiconductor manufacturing equipment, liquid crystal manufacturing equipment, electrical / electronic component manufacturing equipment, food manufacturing equipment, and the like.

It is a block diagram which shows the vacuum processing system which concerns on this invention. It is the schematic which shows the vacuum processing system which concerns on this invention. It is a top view which shows the principal part of the oxygen molecule discharging apparatus which concerns on this invention. It is a schematic structure sectional view explaining the principle of the oxygen molecule discharge device concerning the present invention. It is a schematic plan view which shows the state which has arrange | positioned six oxygen molecule discharge apparatuses which concern on this invention in parallel. It is a schematic side view which shows the state which has arrange | positioned six oxygen molecule discharging apparatuses which concern on this invention in parallel. It is a graph which shows the relationship between exhaust time and a pressure.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Vacuum processing system 12 Vacuum processing container 14 Vacuum pump 16 Extremely low moisture gas production | generation apparatus 18 Sample 20 Oxygen molecule discharge apparatus 22 Load lock 24 Plasma source 28 Raw material gas 30 Raw material cylinder 40 Solid electrolyte 42 Inner electrode 44 Outer electrode 46 Tube 48 Brazing part 50 Container 52 Heater

Claims (11)

A pair of metal tubes;
A thermal expansion coefficient that is respectively connected to the pair of metal pipes and that has a hollow through which gas from the pair of metal pipes passes, and that is the same as the thermal expansion coefficient of the pair of metal pipes A solid electrolyte body made of ceramic that is closely fixed to the pair of metal pipe bodies,
An oxygen molecule discharging device comprising an inner electrode provided on the inner surface of the ceramic solid electrolyte body and an outer electrode provided on the outer surface;
A heating device for heating the oxygen molecule discharging device;
Applying means for applying a voltage between the electrodes of the oxygen molecule discharging apparatus;
An oxygen partial pressure control device that controls the voltage applied between the electrodes of the oxygen molecule discharging device to control the oxygen partial pressure in the gas passing through the hollow;
An extremely low moisture gas generating device for generating a moisture content in the gas to 1 PPB or less;
Said water content of extremely low water vapor in the gas generated by the generating device is introduced following extremely low water vapor 1 ppb, moisture of the inner part is formed by removal processing unit,
A processing system comprising: A pair of metal tubes having the same thermal expansion coefficient as the solid electrolyte body made of zirconia, made of Kovar material, and fixed to the solid electrolyte body by silver brazing;
A solid electrolyte body made of zirconia connected to the pair of metal pipe bodies and having a hollow through which gas from the pair of metal pipe bodies passes;
An oxygen molecule discharging device comprising an inner electrode provided on the inner surface of the zirconia electrolyte body and an outer electrode provided on the outer surface;
A heating device for heating the oxygen molecule discharging device;
Applying means for applying a voltage between the electrodes of the oxygen molecule discharging apparatus;
An oxygen partial pressure control device that controls the voltage applied between the electrodes of the oxygen molecule discharging device to control the oxygen partial pressure in the gas passing through the hollow;
An extremely low moisture gas generating device for generating a moisture content in the gas to 1 PPB or less;
Said water content of extremely low water vapor in the gas generated by the generating device is introduced following extremely low water vapor 1 ppb, moisture of the inner part is formed by removal processing unit,
A processing system comprising: It has the same thermal expansion coefficient as that of the solid electrolyte body made of zirconia, is made of Kovar material, and is fixed to the solid electrolyte body by silver brazing, and the silver brazing fixing portion and the tube are electroplated with gold or platinum. The applied electroplating layer,
A pair of metal tubes comprising an electroless plated layer that has been subjected to electroless gold or platinum plating after pretreatment of the electroplated portion with acid or alkali;
A solid electrolyte body made of zirconia connected to the pair of metal pipe bodies and having a hollow through which gas from the pair of metal pipe bodies passes;
An oxygen molecule discharging device comprising an inner electrode provided on the inner surface of the zirconia solid electrolyte body and an outer electrode provided on the outer surface;
A heating device for heating the oxygen molecule discharging device;
Applying means for applying a voltage between the electrodes of the oxygen molecule discharging apparatus;
An oxygen partial pressure control device that controls the voltage applied between the electrodes of the oxygen molecule discharging device to control the oxygen partial pressure in the gas passing through the hollow;
An extremely low moisture gas generating device for generating a moisture content in the gas to 1 PPB or less;
Processing system water content of the gas the generated with extremely low moisture gas generator is introduced following extremely low water vapor 1 ppb, characterized in that it comprises a processing device and the moisture of the inner portion is formed by removing And the extremely low moisture gas is any one of an etching gas, a sputtering gas, and a carrier gas for an object to be processed. The object to be processed provided inside the processing apparatus is a stainless plate, aluminum plate, alumina plate, glass plate, quartz plate, silicon wafer, insulating film, metal film or semiconductor film, plastic substrate, organic film, or on the substrate. The processing system according to claim 2, comprising at least one of the deposits.   The processing system according to any one of claims 1 to 3, wherein an oxygen partial pressure in the gas is 10 minus 29th atmospheric pressure or less and 10 minus 35th atmospheric pressure or more.   The processing system according to any one of claims 1 to 3, wherein the evacuation and the purge by introducing an extremely low moisture gas having a moisture content of 1 PPB or less are repeated.   Using the treatment system according to any one of claims 1 to 3, moisture is dehydrated and removed from an object to be treated in an atmosphere in which the amount of moisture in the gas is controlled to 1 PPB or less. Processing method of processing object.   A processing method for an object to be processed, wherein the object to be processed is etched in an atmosphere in which the moisture content in the gas is controlled to 1 PPB or less using the processing system according to claim 1.   Depositing a thin film of silicon, aluminum, titanium, hafnium or a compound thin film thereof on a substrate in an atmosphere in which the amount of moisture in the gas is controlled to 1 PPB or less using the processing system according to claim 1 or 2. A method for processing an object to be processed.   A processing method for an object to be processed, wherein the object to be processed is heat-treated in an atmosphere in which the amount of moisture in the gas is controlled to 1 PPB or less using the processing system according to claim 1.   Using the processing system according to claim 1 or 2, the object to be processed is processed using a gas whose water content is controlled to 1 PPB or less as a raw material carrier gas. Method.

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