CN1497677A - Semiconductor device and its manufacturing method and plasma processing device - Google Patents

Semiconductor device and its manufacturing method and plasma processing device Download PDF

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CN1497677A
CN1497677A CNA2003101013852A CN200310101385A CN1497677A CN 1497677 A CN1497677 A CN 1497677A CN A2003101013852 A CNA2003101013852 A CN A2003101013852A CN 200310101385 A CN200310101385 A CN 200310101385A CN 1497677 A CN1497677 A CN 1497677A
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plasma
electrode
plasma discharge
processed substrate
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CN1293608C (en
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宫崎笃
晃继
波多野晃继
酒井道
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Sharp Corp
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Abstract

To obtain a high-quality film even at a low temperature of a substrate to be treated, and to form the film with high efficiency of gas dissociation. A plasma process unit performing plasma treatment to a substrate to be treated 4 is provided with a treatment chamber 5 mounting the substrate to be treated 4 inside, a gas inlet 6 introducing gas into the treatment chamber 5, and a plasma discharge generating part 15 provided in the treatment chamber 5. The plasma discharge generating part 15 has a first electrode 2a and a second electrode 2b provided more adjacently to the substrate to be treated 4 than the first electrode 2a. In the first electrode 2a and the second electrode 2b, only a surface that can be visually inspected from the normal line direction of the substrate to be treated 4 functions as a plasma discharge surface.

Description

Semiconductor device and manufacture method thereof and plasma process device
Technical field
The present invention relates to have the manufacture method of functional electronic device and electronic device.More particularly, the present invention relates to the electronic device that constitutes by semiconductor film, organic membrane and dielectric film etc. and the manufacture method of this electronic device.In addition, the present invention relates to be used to form the plasma process device of films such as semiconductor or conductor.More particularly, the plasma chemical evaporation coating device that relates to the film that is used to make semiconductor film or dielectric film based on plasma excitation chemical vapour deposition technique, the dry etching device that is used for the dry etching that the film pattern of semiconductor film or electrically conductive film forms is removed the plasma process device of the preceding driving device etc. of the resist of use in film pattern forms.
Background technology
Use plasma film forming semiconductor film etc., make the method for electronic devices such as integrated circuit, LCD, organic electroluminescent device, solar cell, be that plasma encourages chemical vapour deposition (CVD) (Chemical Vapor Deposition CVD) method because its convenience or operability are outstanding, therefore in making various electronic devices, use.
(the plasma chemical evaporation coating device is hereinafter referred to as plasma CVD apparatus as the form of the device that uses plasma CVD method.), generally be Figure 33 and form shown in Figure 34.With reference to Figure 33 and Figure 34, plasma CVD apparatus is described.Figure 33 is the skeleton diagram of plasma CVD apparatus in the past, Figure 34 be pattern the profile of plasma CVD apparatus in the past is shown.Plasma CVD apparatus has that use process chamber (vacuum tank) 5 constitutes closes space and electrically insulated from one another and be arranged on electrode 2a, the 2b of two conductor plates formations of relative position abreast therebetween.Make plasma 11 takes place between two plate electrode 2a, 2b, flow through material gas therein, make decomposing gas, disassociation.Film forming semiconductor film etc. above the processed substrate 4 that constitutes by silicon or glass etc. on being installed on a side electrode 2b.
As the method for the plasma 11 that is used to decompose the material gas that film forming uses, the high-frequency electrical energy of general frequency of utilization 13.56MHz.One side's conductor plate electrode 2b adds voltage as earthing potential on relative the opposing party's electrode 2a, make and between two electrode 2a, 2b electric field takes place, and by its insulation breakdown phenomenon, generates plasma 11 as the glow discharge phenomenon.The electrode 2a that adds voltage one side, the electrode 2a that promptly applies electric energy is called negative electrode or sparking electrode.Owing near negative electrode 2a, form very big electric field, therefore promote the disassociation of material gas to generate base (radical) with the electronics in the plasma 11 of its electric field acceleration.Among Figure 34 12 illustrates flowing of base.
Near the part of the discharge 11 of the big electric field of formation the negative electrode 2a is called the negative electrode covered portion.Be diffused into the processed substrate 4 on the electrode 2b of earthing potential at negative electrode covered portion or near generate it base, be deposited on growing film on the surface of substrate 4.The electrode 2b that is positioned at earthing potential is called positive electrode 2b.Near the electric field of size to a certain degree that also forms of positive electrode 2b calls the anode covered portion to this part.Like this, between two electrode 2a, 2b that are parallel to each other, generate plasma, below on the processed substrate 4 on the positive electrode 2b device of film forming call " parallel plate-type device ".
Be extensive use of in the electronic device that this plasma CVD method is made in various industries.For example, in the manufacturing process of the LCD of active-drive, make the switch element that is called as TFT (thin-film transistor).In TFT, as its component part, gate insulating films such as amorphous silicon film or silicon nitride film play important effect.In order to make each film play its effect, the technology of the high-quality transparent insulating film of film forming is indispensable efficiently.In addition, for example, in order to make organic electroluminescent device, in film forming after the organic film, be exposed to the diaphragm on the surface in the atmosphere as protection, the technology of the high-quality transparent insulating film of film forming is indispensable efficiently.And then, for example in order to make solar cell, in film forming after the solar cell layer, be exposed to the diaphragm on the surface in the atmosphere as protection, the technology of film forming high quality film is indispensable efficiently.The electronic device of Zhi Zuoing is current so uses widely.
Known, material gas is changed to etchant gas, plasma 11 takes place in the same manner with plasma CVD apparatus, carry out film corrosion the dry etching device or carry out the preceding driving device that resist removes and also be referred to as plasma process device.The generation etc. of the method for generation of plasma 11 or base is identical with the mechanism of plasma CVD apparatus, and the base that has arrived processed substrate 4 carries out the removal of film etc.The dissimilarity of dry etching device or preceding driving device and plasma CVD apparatus just is not only to exist base, also utilizes in its corrosion action based on the physical sputtering of isoionic bombardment by ions or to the energy incident this point of processed substrate 4.
In the plasma CVD apparatus of in the past establishing, has boundary, when large area electron devices such as making LCD or amorphous solar cell, when processed substrate 4 carries out film forming, be difficult to sometimes carry out the disassociation of material gas fully and obtain high-quality film.For example, in known in the past parallel plate-type device, the disassociation of material gas is insufficient sometimes.Under the situation of film forming silicon nitride film, use silane (SiH as material gas 4), ammonia (NH 3), nitrogen (N 2), hydrogen (H 2) etc., cracked ammonium carries out the supply of nitrogen to film.But, for example if in copper wiring the film forming silicon nitride film, then ammonia gas might make copper corrosion.
In addition, ammonia is the strong gas of chemism, wishes sometimes not use ammonia, and only uses nitrogen film forming silicon nitride film.In this case, in the parallel plate-type device, the hydrogen or the nitrogen that are difficult to dissociate be can not decompose fully, dielectric film or the outstanding silicon nitride film of diaphragm are difficult to obtain.Perhaps, when the film forming amorphous silicon film, use silane, hydrogen etc. as material gas, and the utilization ratio of gas is limited to about 10%.In this case, in the parallel plate-type device, we can say the disassociation that can not promote material gas fully.
Be disclosed in each document etc. of following explanation to the technology of processed substrate 4 film forming high quality film.
For example, open in the flat 11-144892 communique in the disclosed plasma apparatus the spy, constitute the sparking electrode relative with glass substrate by a plurality of electrodes, each electrode is configured to add the high frequency voltage of mutual opposed polarity, makes the discharge that transverse direction takes place.Reacting gas is emitted in the middle of electrode and electrode.The gas that is released in the plasma discharging of transverse electric field has produced after the plasma reaction, and the direction diffusion along glass substrate one side is deposited on the glass substrate.Thus, can on glass substrate, not produce the discharge damage, carry out high-quality film forming.But, also identical in this plasma apparatus with the parallel plate-type device, can not promote the disassociation of material gas.
The technology of the disassociation of promotion material gas for example is disclosed in the spy and opens in the flat 1-279761 communique.Open in the flat 1-279761 communique in the disclosed plasma apparatus the spy, concave shaped space is set in negative electrode, improve plasma density according to the hollow cathode effect.Thus, promote the disassociation of material gas, compare, can obtain film forming speed at a high speed with common parallel plate-type device.But in this device, owing to being exposed to the sun in plasma in the surface of processed substrate, so film forming face is subjected to plasma damage.
By the design temperature of processed substrate 4 is taken as more than 300 ℃, can the such plasma damage of enough heat energy reparations.But, be set in processed substrate 4 about 200 ℃ or under the situation of its following temperature in hope, can not keep good membranous.That is, use plasma CVD apparatus, can't under low especially processed substrate temperature, establish and realize high quality film, carry out the method for film forming with very high gaseous dissociation efficient.
Supposed in dry etching device or preceding driving device, to use the special situation of opening the structure of the plasma apparatus of putting down in writing in the flat 11-144892 communique.In this case, can control plasma generating unit and bombardment by ions control unit respectively.That is, the 3rd electrode is installed in the back of substrate 4, can takes place separately, carry out the control of bombardment by ions, can improve parameter control with plasma.
But, can not promote to handle the disassociation of gas in this case, can not bring up to certain to processing speed more than the certain value.That is, in a word, can not establish the plasma process device that moves with high-performance and very high gaseous dissociation efficient.
Up to now, with the film of above such technology film forming as device with obtaining sufficient diaphragm characteristic.For example, in organic electroluminescent device,, the diaphragm of transparent insulating need be set at the skin of element in order to prevent the water vapour in the atmosphere or the intrusion of oxygen.Therefore organic membrane in the element need form diaphragm at this because in the processing temperature more than 100 ℃, characteristic worsens significantly below the temperature.
But, in plasma CVD apparatus in the past, under such temperature conditions, can not form the second best in quality diaphragm.For example; at the 2229th page to the 2231st page (Applied Physics Letters of Applied Physics communication the 65th volume; volume 65; pages 2229-2231) in; reported when having formed silicon nitride film with 100 ℃ as diaphragm; because membranous deterioration, so the water vapour in the atmosphere invades in the film, produces combining of silicon and oxygen.According to this report, it is contemplated that water vapour or oxygen see through film eventually.Under current situation, actual situation is owing to only can realize inferior diaphragm, therefore for the isolation of atmosphere, with the glass substrate of using at the bottom of the nitrogen-sealed pipe.As the device that silicon nitride film is used as diaphragm, polysilicon solar cell or gallium arsenic family electronic device are arranged, also exist problem on the above-mentioned quality of enumerating about these devices.
The present invention produces in view of above each point, and its main purpose is to improve the precision of plasma treatment by promoting decomposition and the disassociation based on isoionic gas, improves the quality of the electronic device of manufacturing.
Summary of the invention
Plasma process device of the present invention is a plasma process device of implementing plasma treatment on processed substrate, has possessed in inner mounting the process chamber of above-mentioned processed substrate; In above-mentioned process chamber, import the gas introduction port of gas; Be arranged on the plasma discharge generating unit in the above-mentioned process chamber, the 2nd electrode that above-mentioned plasma discharge generating unit has the 1st electrode and is provided with than the more approaching above-mentioned processed substrate of above-mentioned the 1st electrode, above-mentioned the 1st electrode and above-mentioned the 2nd electrode play has only the effect as the plasma discharge face of the face that can discern from the normal direction of above-mentioned processed substrate.
In addition, plasma process device of the present invention is a plasma process device of implementing plasma treatment on processed substrate, has possessed in inner mounting the process chamber of above-mentioned processed substrate; In above-mentioned process chamber, import the gas introduction port of gas; Be arranged on the plasma discharge generating unit in the above-mentioned process chamber, above-mentioned plasma discharge generating unit has the 1st electrode; Be formed on the insulating barrier on the part of electrode surface of above-mentioned the 1st electrode; Be formed on the 2nd electrode on the above-mentioned insulating barrier.
The above-mentioned gas introducing port is preferably disposed on above-mentioned the 1st electrode one side.In addition, the plasma discharge face of above-mentioned the 1st electrode concave preferably.And then the area of plasma discharge face that the area of the plasma discharge face of above-mentioned the 1st electrode cans be compared to most above-mentioned the 2nd electrode is big.
Above-mentioned plasma discharge generating unit preferably has the plasma discharge face district of a plurality of above-mentioned the 1st electrodes and the plasma discharge face district of above-mentioned the 2nd electrode respectively.In addition, direction along a face of above-mentioned processed substrate alternately forms the plasma discharge face district of a plurality of above-mentioned the 1st electrodes and the plasma discharge face district of above-mentioned the 2nd electrode, and more than the interelectrode distance of above-mentioned the 2nd electrode that preferably adjoins each other of the distance between above-mentioned the 2nd electrode and the above-mentioned processed substrate.
And then also having the power supply that on above-mentioned the 1st electrode and above-mentioned the 2nd electrode, applies electric energy, the frequency of above-mentioned power supply is effective below the above 300MHz of 100kHz.
In addition, the manufacture method of electronic device of the present invention is to use and has possessed in inner mounting the process chamber of above-mentioned processed substrate; In above-mentioned process chamber, import the gas introduction port of gas; Be arranged on the plasma process device of the plasma discharge generating unit in the above-mentioned process chamber, make the method for electronic device, be included in the technology of the above-mentioned processed substrate of inside mounting of above-mentioned process chamber; In mounting in the above-mentioned process chamber of above-mentioned processed substrate, import the technology of above-mentioned gas from the above-mentioned gas introducing port; By above-mentioned plasma discharge generating unit generation plasma discharge, implement the technology of plasma treatment on the surface of above-mentioned processed substrate, along the discharge path importing above-mentioned gas of above-mentioned plasma discharge.
In addition, the manufacture method of electronic device of the present invention is to use plasma treatment appts of the present invention to make the method for electronic device, is included in the technology of the above-mentioned processed substrate of inside mounting of above-mentioned process chamber; In mounting in the above-mentioned process chamber of above-mentioned processed substrate, import the technology of above-mentioned gas from the above-mentioned gas introducing port; By above-mentioned plasma discharge generating unit generation plasma discharge, implement the technology of plasma treatment on the surface of above-mentioned processed substrate.
In addition, electronic device of the present invention be on insulated substrate film forming the electronic device of dielectric film, above-mentioned dielectric film comprises silicon, nitrogen and hydrogen, the hydrogen binding capacity in the above-mentioned dielectric film is 7 * 10 21Cm -3More than.Oxygen binding capacity in the above-mentioned dielectric film in fact preferably 0.Above-mentioned dielectric film is preferably formed as and is skin.Above-mentioned insulated substrate also can be formed by organic material.In addition, can also have organic layer.
In addition, the plasma discharge mask of above-mentioned the 1st electrode of plasma process device of the present invention has the curvature portion of spill.
The plasma discharge face of above-mentioned the 1st electrode and the plasma discharge face of above-mentioned the 2nd electrode preferably constitute the part of continuous curve surface.
On the plasma discharge face of above-mentioned the 1st electrode, can also form a plurality of recess.And then gas introduction port is formed on the bottom that is preferably in the above-mentioned recess of at least a portion.
The plasma discharge face of can also sandblast processing above-mentioned the 1st electrode.
A plurality of recesses towards processed base openings preferably are set on above-mentioned the 1st electrode.And then the opening shape of above-mentioned recess is quadrangle preferably.In addition, the opening shape of above-mentioned recess also can be circular.
In addition, plasma process device of the present invention is to have possessed in inner mounting the process chamber of processed substrate; Import the gas introduction port of gas in the inside of above-mentioned process chamber; Be arranged on the plasma process device of the plasma discharge generating unit of above-mentioned inner treatment chamber, above-mentioned plasma discharge generating unit possesses a plurality of insulated parts that are the extension of strip ground along the direction parallel with above-mentioned processed substrate; At least the 1st electrode that between the above-mentioned insulated part that adjoins each other, is provided with; The 2nd electrode that is provided with state in the end of above-mentioned processed substrate one side of above-mentioned each insulated part with above-mentioned the 1st electrode separation.
Each the 1st electrode that is provided with between above-mentioned each insulated part also can be separated from each other.
In addition, plasma process device of the present invention is to have possessed in inner mounting the process chamber of processed substrate; Import the gas introduction port of gas in the inside of above-mentioned process chamber; Be arranged on above-mentioned inner treatment chamber, implement the plasma process device of the plasma discharge generating unit of plasma treatment on above-mentioned processed substrate, above-mentioned plasma discharge generating unit possesses a plurality of insulated parts that are the extension of strip ground along the direction parallel with above-mentioned processed substrate; At least the 1st electrode that between the above-mentioned insulated part that adjoins each other, is provided with; The 2nd electrode that is provided with state in the end of above-mentioned processed substrate one side of above-mentioned each insulated part with above-mentioned the 1st electrode separation, form a plurality of gas introduction ports in above-mentioned the 1st electrode, the direction of intersecting along the length direction for the insulated part of above-mentioned strip is arranged above-mentioned a plurality of gas introduction port is set.
Above-mentioned a plurality of gas introduction port is preferably along arranging with the direction of the length direction quadrature of above-mentioned insulated part.
Above-mentioned each gas introduction port can also constitute along the direction blow gas that is parallel to each other.
Above-mentioned each gas introduction port preferably constitutes along the direction blow gas vertical with the plasma discharge face of above-mentioned the 1st electrode.
Above-mentioned each gas introduction port can also constitute the direction blow gas for the normal direction inclination of processed substrate.
The effect of invention
If according to plasma process device of the present invention, even then because under low processed substrate temperature, also can be suppressed to the plasma damage of face, and promotion is based on the decomposition and the disassociation of isoionic gas, therefore can improve the precision of plasma treatment, the quality of the electronic device of raising manufacturing etc.
Description of drawings
Fig. 1 be pattern the stereogram of the plasma CVD apparatus of example 1 is shown.
Fig. 2 be pattern the profile of the plasma CVD apparatus of example 1 is shown.
Fig. 3 illustrates the discharge path of material gas pressure ratio when higher.
Fig. 4 illustrates the discharge path of material gas pressure ratio when low.
Fig. 5 be pattern the plane graph that is connected of high frequency electric source and positive electrode 2b is shown.
Fig. 6 be pattern the stereogram of the plasma CVD apparatus of example 2 is shown.
Fig. 7 be pattern the profile of the plasma CVD apparatus of example 2 is shown.
Fig. 8 is the profile of a part that the plasma discharge generating unit of example 2 is shown enlargedly.
Fig. 9 be pattern the profile of organic electroluminescent device is shown.
Figure 10 is the figure suitable with Fig. 8 that the plasma discharge generating unit of example 4 is shown enlargedly.
Figure 11 is the figure suitable with Figure 10 that the plasma discharge generating unit of example 5 is shown enlargedly.
Figure 12 is the figure suitable with Figure 10 that the plasma discharge generating unit of example 6 is shown enlargedly.
Figure 13 is the figure suitable with Figure 10 that the plasma discharge generating unit of example 7 is shown enlargedly.
Figure 14 is the figure suitable with Figure 10 that the plasma discharge generating unit of example 8 is shown enlargedly.
Figure 15 is the stereogram that the plasma discharge generating unit of example 9 is shown.
Figure 16 is the stereogram that the plasma discharge generating unit of example 10 is shown enlargedly.
Figure 17 is the stereogram that the plasma discharge generating unit of example 11 is shown.
Figure 18 is the plane graph that the plasma discharge generating unit of example 11 is shown.
Figure 19 is the stereogram that the plasma discharge generating unit of example 12 is shown.
Figure 20 is the plane graph that the plasma discharge generating unit of example 12 is shown.
Figure 21 illustrates the plasma discharge generating unit of example 13 and the stereogram of processed substrate 4.
Figure 22 is the profile that the plasma discharge generating unit of example 13 is shown enlargedly.
Figure 23 is the figure suitable with Figure 22 that the plasma discharge generating unit of example 14 is shown enlargedly.
Figure 24 is the figure suitable with Figure 22 that the plasma discharge generating unit of example 15 is shown enlargedly.
Figure 25 is the figure suitable with Figure 22 that the plasma discharge generating unit of example 15 is shown enlargedly.
Figure 26 illustrates the discharge path of the example 16 of material gas pressure ratio when higher.
Figure 27 illustrates the discharge path of the example 16 of material gas pressure ratio when low.
Figure 28 is the profile that the plasma discharge generating unit of example 17 is shown enlargedly.
Figure 29 is the profile that the plasma discharge generating unit of example 18 is shown enlargedly.
Figure 30 is the profile that the plasma discharge generating unit of example 19 is shown enlargedly.
Figure 31 is the approximate three-dimensional map that the plasma discharge generating unit of example 20 is shown.
Figure 32 is the profile that the plasma discharge generating unit of example 21 is shown enlargedly.
Figure 33 is the skeleton diagram of plasma CVD apparatus in the past.
Figure 34 be pattern the profile of plasma CVD apparatus in the past is shown.
Embodiment
Below, with reference to description of drawings example of the present invention.And the present invention is not limited to following example.
Working of an invention form 1
The structure of plasma CVD (chemical vapor deposition) device of explanation the invention process form 1 while seeing figures.1.and.2.Fig. 1 is a stereogram of schematically representing the plasma CVD apparatus of example 1, and Fig. 2 is a sectional drawing of schematically representing the plasma CVD apparatus of example 1.
Plasma CVD apparatus has and processed substrate 4 can be placed on inner process chamber (vacuum tank) 5, material gas is imported gas introduction port 6 in this process chamber 5.As typical form, the substrate holder 9 that is used to keep processed substrate 4 is being set in process chamber 5, processed substrate 4 is placed on the substrate holder 9.In addition, substrate holder 9 is with respect to treatment substrate 4, can carry out necessary correspondence according to direct voltage or alternating voltage and apply bias voltage.
In the outside of process chamber 5,15 supply capabilities that is the high frequency electric source 1 that apply electric energy of article on plasma discharge generating unit is being set, to process chamber 5 in, is supplying with the gas supply part 13 of material gas (following also abbreviate as " gas "), the gas discharge section 10 of the discharge of the gas in the process chamber 5.As gas discharge section 10, for example, adopt mechanical type booster pump or rotary pump.High frequency electric source 1 is connected with plasma discharge generating unit 15 by distribution 8.
Plasma discharge generating unit 15, separated by a distance with processed substrate 4 and be arranged in the process chamber 5 in the mode relative with substrate 4, and have negative electrode (negative electrode) 2a as the 1st electrode, at positive electrode (anode) 2b of insulated part between the electrode that forms on a part of electrode surface of negative electrode 2a (below, be also referred to as " insulating barrier " or " insulated part ") 3, conduct the 2nd electrode that on insulating barrier 3, forms.Positive electrode 2b is arranged to the more approaching processed substrate 4 than negative electrode 2a.
In this example, a direction in the surface direction of processed substrate 4 (direction of one side) is being provided with a plurality of positive electrode 2b by strip.According to this configuration, can alternately be concatenated to form the zone of the plasma discharge face of the zone of plasma discharge face of negative electrode 2a and positive electrode 2b at grade.And about the plasma discharge face, will illustrate below.
Negative electrode 2a is provided with the gas introduction port 6 that connects negative electrode 2a on thickness direction.After 7 temporary transient delays, import in the process chamber 5 in gas hold-up portion from gas supply part 13 gas supplied by gas introduction port 6.
The detailed structure of plasma discharge generating unit 15 is as follows.
Promptly, plasma discharge generating unit 15, have the insulating barrier 3 that on the direction parallel, extends by strip with processed substrate 4, at least be located at negative electrode 2a between each adjacent insulating barrier 3, with the state of isolating with negative electrode 2a be located at insulating barrier 3 by the positive electrode 2b on the end of processed substrate 4 one sides.
Tabular negative electrode 2a disposes abreast with processed substrate 4.Interval between adjacent each insulating barrier 3 is equal to each other.The upper surface of each insulating barrier 3 is covered by positive electrode 2b.In other words, positive electrode 2b presses strip formation too.So, in plasma discharge generating unit 15, formed the groove 18 that a plurality of sections are concave shape by the upper surface of 2 sides of insulating barrier 3 that faces with each other and positive electrode 2b and the negative electrode 2a that exposes betwixt.Negative electrode 2a in the groove 18 constitutes the plasma discharge face.In addition, in above-mentioned groove 18, be spaced a plurality of gas introduction ports 6 of formation in accordance with regulations along the ditch length direction.Each gas introduction port 6 is located at the middle position of the ditch cross direction of groove 18.
When making plasma discharge generating unit 15, for example, as shown in Figure 1, preparing rectangle, length that a plurality of section configurations are 5mm * 3mm is the aluminium bar of 300cm.In addition, preparing size is the aluminium sheet of 3mm for 110cm * 110cm, thickness.To be configured on the aluminium sheet as negative electrode 2a in the mode of mutual almost parallel as a plurality of aluminium bars of positive electrode 2b.Between aluminium bar and the aluminium sheet, be arranged to electric insulation each other.Specifically, negative electrode 2a and positive electrode 2b are isolated mutually, and form insulated part between electrode (insulating barrier) 3 in its space by being clipped in as the aluminium oxide of insulant.Distance between electrode between the height of insulated part 3 that is negative electrode 2a and the positive electrode 2b is 10mm.Below, the substrate that will have insulated part 3 between negative electrode 2a, positive electrode 2b and electrode is called " electrode base board ".Electrode base board, whole size is 110cm * 110cm, wherein, the size of plasma discharge generating unit 15 is 100cm * 100cm.In addition, negative electrode 2a also can form with whole member.
In the direction of extending with positive electrode 2b roughly on the section of the direction of quadrature, the width d1 of insulated part 3 is 5mm between positive electrode 2b and electrode, the width d2 of negative electrode 2a is 10mm, the height d3 of insulated part 3 is 10mm between electrode, and insulated part 3 is spaced apart 15mm spacing (pitch) between each positive electrode 2b and electrode.High frequency voltage is applied on the aluminium sheet of electrode base board.Aluminium sheet plays a part negative electrode 2a, will be across between electrode insulated part 3 and be set at earthing potential with the aluminium bar of aluminium sheet insulation, and used as positive electrode 2b.
As processed substrate 4, at the glass substrate that to be provided with a thickness on the position of 20mm above the positive electrode 2b be 1.1mm.Be provided with in the back of substrate holder 9 (with processed of processed substrate 4 an opposite side) and be used for heater (not shown) that processed substrate 4 is heated.Processed substrate 4 for example is heated to and makes its temperature reach 200 ℃.
Plasma discharge generating unit 15 produces discharge (plasma) 11 according to the voltage (potential difference) that is applied between positive electrode 2b and the negative electrode 2a.By making gas flow into plasma discharge generating unit 15, make gas cracking disassociation and the generation atomic group.The flow direction of the expression of 12 among Fig. 2 atomic group.The atomic group that is generated is diffused into processed substrate 4, and adheres on the substrate 4 that is deposited on by substrate holder 9 maintenances.That is, film is grown on the surface of substrate 4 and form film.
The atomic group that is generated arrives film surface in rapid succession, thereby the thickness of film is constantly increased.When continuing to apply voltage after reaching the thickness that sets, will the voltage between positive electrode 2b and the negative electrode 2a be applied (electric power of article on plasma discharge generating unit 15 is supplied with) and stop.In this manner, plasma treatment is carried out on the surface of processed substrate 4.After this, processed substrate 4 is being taken off and when process chamber 5 took out, the film that can have been formed film formed substrate from substrate holder 9.
Below, illustrate this example plasma CVD apparatus action and adopted the electronic device manufacturing method of plasma CVD apparatus.In addition, also actual fabrication the plasma CVD apparatus of this example, and provide the operation result of this device hereinafter.The concrete numerical value that below provides is only represented the situation of one embodiment of the invention, is not that the present invention is had any qualification.In addition, operation result applies bias voltage on processed substrate 4 hereto.
The material gas of using is SiH 4(200sccm), H 2(10slm) and N 2(20slm).Here, so-called " sccm " is to be the gas flow that unit flows through with " cubic centimetre/minute " under 0 ℃.In addition.So-called " slm " is to be the gas flow that unit flows through with " rise/minute ".As shown in Figure 2, carried out the importing of material gas from the gas introduction port 6 that is arranged on the negative electrode 2a.For applying electric energy, used the high frequency electric source 1 of frequency 13.56MHz.
In device illustrated in figures 1 and 2, by gas pressure being set at 200Pa, high frequency power is set at 7kW and changes substrate temperature having formed silicon nitride film.The membranous of formed silicon nitride film estimated.It is the results are shown in table 1.The film forming speed of silicon nitride film is 0.4nm (4 )/second, and the film thickness uniformity in the film is ± 3%.
On the other hand, for comparing, Figure 33 and device shown in Figure 34 have also been carried out same operation test.Figure 33 and device shown in Figure 34 are some, identical with the device of this example except that following.Figure 33 and device shown in Figure 34 are the parallel plate-type device, carry out film forming by negative electrode 2a is applied high frequency power and handle on the glass substrate that is provided with on the positive electrode 2b relative with it.Interelectrode distance is 20mm.
Membranous parameter in the table 1 is measured as follows.Resistivity is to calculate by being determined at the electric current that flows through when film thickness direction applies the electric field of 1MA/cm.The unit of resistivity is Ω cm.Below, more detailed assay method is described.Handle conductive boards such as the conductive board of end on the glass substrate of usefulness placing membranous mensuration usefulness, for example P type silicon chip in film forming.The glass substrate of film forming being handled usefulness carries out film forming with conductive board to be handled.On formed film, metallic films such as AM aluminum metallization, chromium or titanium.At the voltage that applies between conductive board and the metallic film below about 500V, measure the Weak current that flows through, and the calculated resistance rate.Perhaps, also can not carry out the evaporation of metallic film, but employing contacts mercury and applies voltage method by mercury with face.
The hydrogen binding capacity utilizes fourier transform infrared spectroscopy, identifies according to the binding capacity of silicon and hydrogen and the binding capacity of nitrogen and hydrogen.The unit of hydrogen binding capacity is cm -3The oxygen binding capacity is based on the relative intensity of fourier transform infrared spectroscopy, and is the relative value of the bonding spectral intensity of silicon and oxygen to the bonding spectral intensity of silicon and nitrogen.Below, the more detailed assay method to hydrogen binding capacity and oxygen binding capacity is described.The same when measuring resistivity, handle conductive boards such as the conductive board of end on the glass substrate of usefulness placing membranous mensuration usefulness, for example P type silicon chip in film forming.The glass substrate of film forming being handled usefulness carries out film forming with conductive board to be handled.Carry out the Fourier transform processing by the irradiation infrared laser and to its interference waveform, according to of the absorption of wave number spectroscopic assay film to infrared light.Then, can be according to the peak value (2150cm that causes by hydrogen bond -1Near and 3350cm -1Near) and the peak value (1070cm that causes by the oxygen key -1Near) intensity try to achieve separately binding capacity.The bonding spectral intensity of bonding spectral intensity, silicon and the oxygen of the binding capacity of nitrogen and hydrogen, silicon and nitrogen for example can be measured with reference to the document of 53～55 pages of the strong works of Jing Cun, " evaluation of amorphous thin film " (1989, upright publishing company) altogether.
As other assay methods of hydrogen binding capacity, adopt the method and the secondary ion mass spectrometry with halogen labeling of gas chromatography in the time of can enumerating sample heating (reaching hundreds of degree).According to secondary ion mass spectrometry with halogen labeling, measuring resolution capability is hundreds of μ m, thereby the depth direction of film also can analyze, so, even the film of determination object also can be analyzed when being the formation film of device.
As shown in table 1, for resistivity,, can obtain the insulating film all high than parallel plate-type device in each humidity province according to this example.It is generally acknowledged, so this is can form high-quality film because the film forming processing of plasma damage can take place in device of the present invention hardly, in contrast, in the parallel plate-type device, plasma damage to film forming face is inevitable, thereby is difficult to obtain well membranous.
Under the situation of this example, the hydrogen binding capacity is roughly certain value in each humidity province, and different therewith, under the situation of parallel plate-type device, the hydrogen binding capacity reduces significantly when the temperature of processed substrate 4 is 100 ℃.As its reason, be commonly considered as the few cause of disassociation amount of hydrogen molecule under the situation of parallel plate-type device.In detail, its reason can think, when the temperature of processed substrate 4 is high, hydrogen atom spread, so can make the suspension key (dangling bond) of hydrogen proceed to end fully on the film surface.But when the temperature of processed substrate 4 was hanged down, the distance that hydrogen atom can spread on the film surface reduced, and original disassociation amount did not proceed to end fully with regard to the branch of Cheng Jian is very difficult in the hydrogen atom seldom, thereby the suspension key will remain in the film.When in film, having the suspension key, not only make membranous step-down, and be difficult to the long-time stability of maintenance as film.
Plasma CVD apparatus according to this example, the disassociation amount of hydrogen molecule is many, so, can think, even the distance that the temperature of processed substrate 4 is low, hydrogen atom can spread reduces, also can proceed to the end of suspension key fully with regard to a lot of hydrogen atoms by original disassociation amount on the film surface.Therefore, by the electronic device that the plasma CVD apparatus of this example obtains, the hydrogen binding capacity in the dielectric film is more than existing device.For example, as shown in table 1, the hydrogen binding capacity in the dielectric film is 7 * 10 21Cm -3More than, ideally, can obtain 1 * 10 22Cm -3Above electronic device.
Table 1
Example 1 The parallel plate-type device
Processed substrate temperature 300℃ ?200℃ ?100℃ ?300℃ ?200℃ ?100℃
Resistivity (Ω cm) 1.2×10 13 ?6.2×10 13 ?1.0×10 14 ?3.3×10 12 ?1.7×10 13 ?3.6×10 11
Hydrogen binding capacity (cm -3) 1.0×10 22 ?7.0×10 21 ?1.0×10 22 ?4.6×10 21 ?5.5×10 21 ?2.1×10 20
Oxygen binding capacity (initial stage) 0 ?0 ?0 ?0 ?0 ?0
Oxygen binding capacity (after 1 month) 0 ?0 ?0 ?0.1 ?0.1 ?0.4
About the oxygen key,, all do not observe at the manufacturing initial stage, thereby the oxygen binding capacity is 0 no matter at this example or under the situation of parallel plate-type device.But, in atmosphere, place in the mensuration after 1 month, under the situation of parallel plate-type device, observe the oxygen key.Its binding capacity increases with membranous deterioration.And in this example, even also do not observe the oxygen key in the mensuration after 1 month.Therefore, according to the device of the plasma CVD of this example, the transparent insulating film that can obtain having good diaphragm characteristic.This dielectric film is formed the skin electronic device of (being called outermost layer, as follows), can keep long-term stability.
During state in the reative cell after observing film forming, be under 100 ℃ the situation in the temperature of the processed substrate 4 of parallel plate-type device, can observe much powder as product.This powder is commonly considered as the polymer of silane.As everyone knows, when producing powder, powder will enter in the formed film, thereby make membranous deterioration.In this example, in each humidity province, all almost can't see powder, so, even also demonstrate good device performance from this viewpoint.
The plasma CVD apparatus of this example in each electrode surface of negative electrode 2a and positive electrode 2b, has only the effect of face (part) the plasma discharge face that can see from the normal direction of processed substrate 4.In other words, negative electrode 2a still is that positive electrode 2b has the structure that can see its whole plasma discharge faces from processed substrate 4 sides.Here, so-called plasma discharge face not only means the surface of the member that uses on electrode 2a, 2b, and is the surface that in fact plays the sparking electrode effect that is exchanging plasma portion and charged particle (electric charge).
Specifically, positive electrode 2b by the face of negative electrode 2a one side and with the zone of the formation region overlapping of positive electrode 2b in the face of negative electrode 2a, all be the face that can not see from processed substrate 4 sides.Since positive electrode 2b by the face of negative electrode 2a one side and and the zone of the formation region overlapping of positive electrode 2b in the face of negative electrode 2a between exist insulated part 3 between electrode, so the face by negative electrode 2a one side of positive electrode 2b reaches and the face of the negative electrode 2a that the zone of the formation region overlapping of positive electrode 2b is interior, does not play the plasma discharge face.
When between two electrode 2a, 2b, not having between electrode insulated part 3, positive electrode 2b by the face of negative electrode 2a one side and with the zone of the formation region overlapping of positive electrode 2b in the face of negative electrode 2a, all will have the function of plasma discharge face.When in this state negative electrode 2a being applied high frequency power, main discharge occurs in leaning between the face of negative electrode 2a one side of negative electrode 2a surface and positive electrode 2b.But, even the plasma that produces in this space makes material gas disassociation, the most of atomic group after the disassociation also will be as film and attached to positive electrode 2b by on the face of negative electrode 2a one side.Therefore, film forming speed can not be brought up to the degree that hope reaches, so, the disposal ability as device has been produced restriction.Plasma CVD apparatus according to this example illustrated in figures 1 and 2, since be the structure that can see the whole electrode surfaces that play the effect of plasma discharge face from processed substrate 4 sides, the processed substrate 4 so the atomic group major part after the disassociation can both lead effectively.
As depicted in figs. 1 and 2, employing can see that another advantage of the structure of the whole electrode surfaces that play the effect of plasma discharge face is from processed substrate 4 sides, but is the setting range of having expanded pressure.Under the situation of Figure 33 and parallel plate-type device shown in Figure 34, owing to structurally determined interelectrode distance, so interelectrode distance is exactly a discharge path length itself, thereby is easy to produce isoionic material gas pressure and will be limited in certain certain scope.This is because the cause of the domination of the Paschen's law of knowing in the engineering of being discharged.So-called Paschen's law, it is a kind of like this law, promptly, the space electric field intensity that can begin to discharge by the decision of the product of material gas pressure and discharge path length, and obtain in the minimum of this product value for the space electric field intensity that can begin to discharge under the situation of certain value, and rise being greater than or less than the space electric field intensity that can begin to discharge under the situation of this product value.
On the other hand, when adopting structure illustrated in figures 1 and 2, the electrode surface of two electrode 2a, 2b is not relative each other, and the path of the discharge of Chan Shenging betwixt as shown in Figure 3 and Figure 4, shortens or elongated with the height of material gas pressure.11b among Fig. 3 and Fig. 4, the typical path of expression discharge.Under the situation of Fig. 3, material gas pressure is higher, thereby discharge path shortens.Under the situation of Fig. 4, material gas pressure is lower, thereby discharge path is elongated.
In addition, the electrode surface of two electrode 2a, 2b does not also have an advantage at grade.Specifically, with the electrode surface of two electrode 2a, 2b roughly at grade situation (for example, with reference to the spy open 2001-338885 communique, spy open the 2002-217111 communique, and the spy open the 2002-270522 communique) compare, discharge path has increased the height that roughly is equivalent to insulated part 3 between electrode, so the dissociation efficiency of gas increases.Further,, can adjust the distance of discharge path by adjusting the height of insulated part 3 between electrode, so, the high advantage of the adjustment degree of freedom of material gas pressure also had.As mentioned above, broaden by changing the length of discharge path, can make the pressure limit that is easy to produce isoionic material gas.
As the position that gas introduction port 6 is set.As depicted in figs. 1 and 2, preferably be located at negative electrode 2a side.In the device of this example, negative electrode 2a is far away from processed substrate 4 than positive electrode 2b.Therefore, by import gas from negative electrode 2a side, air-flow 14 substrates 4 that lead stably.In addition, between negative electrode 2a and positive electrode 2b, exist plasma area, thereby material gas is flowed along the discharge path of plasma discharge.Therefore, prolong, can promote the disassociation of gas by the distance that material gas is flowed in plasma.
The area of the plasma discharge face of negative electrode 2a is more preferably greater than the area of the plasma discharge face of positive electrode 2b.It is the reasons are as follows.In the parallel plate-type device, the electric field of anode covering part is littler than negative electrode covering part.Even this be since the area of two electrode 2a, 2b about equally and the wall of periphery etc. also are in the earthing potential identical with positive electrode 2b, so, in fact make the area of the total area of earthing potential portion greater than negative electrode 2a.Therefore, the area of the plasma discharge face by making negative electrode 2a can increase the electric field of anode covering part greater than the area of the plasma discharge face of positive electrode 2b.In this state, not only also can promote the disassociation of gas, further increase thereby make as overall gaseous dissociation amount in the negative electrode covering part but also in the anode covering part.
In this example, repeat distance between adjacent positive electrode 2b that is the spacing of positive electrode 2b are 15mm, and the distance between the surface of positive electrode 2b and processed substrate 4 is 20mm.In this case, film thickness distribution is in ± 3%.But, even as the distance between the surface of positive electrode 2b and processed substrate 4 is changed to 14mm, also it is shorter than spacing of positive electrode 2b, then film thickness distribution is ± 8%, thereby will obtain wavy film thickness distribution according to the formation pattern of electrode 2a, 2b.As depicted in figs. 1 and 2, positive electrode 2b has the pattern of strip, so importantly can not be with this pattern transfer for becoming film figure.For this reason, the distance between the surface of positive electrode 2b and processed substrate 4 is more preferably greater than the repeat distance between positive electrode 2b.
In this example, shown in Fig. 5 (a), per 1 of a plurality of bar-shaped positive electrode 2b is connected with high frequency electric source 1 by distribution 8 in the end, but device of the present invention is not limited thereto.For example, shown in Fig. 5 (b), also can be linked together, and the distribution 8 that will connect from power supply 1 is connected with the bar of this connection usefulness with the bar of identical material a end with a plurality of bar-shaped positive electrode 2b.Perhaps, shown in Fig. 5 (c), all use the bar of identical material to connect two ends of a plurality of bar-shaped positive electrode 2b, and the distribution 8 that will connect from power supply 1 is connected with the bar of this connection usefulness.
Be used to keep the treatment substrate seat 9 of processed substrate 4, in Fig. 1, only keeping the end of processed substrate 4, therefore, make processed substrate 4 be in floating potential.On the other hand, for example, in the behind of processed substrate 4 conductor plate is set closely sometimes in face for substrate temperature is evenly distributed.In this case, conductor plate can be a floating potential, also can be earthing potential.The reason of can be not the current potential of processed substrate 4 not being carried out special consideration is, because the location of plasma 11 and processed substrate 4 at intervals, disperse to processed substrate 4 so only make at the atomic group that is neutrality on the electric charge.Under the situation of the film-forming process that need carry out bombardment by ions to a certain degree to substrate surface, by behind conductor plate is set at processed substrate 4, can also control its current potential effectively.In this case, can attract ion beams from intervals plasma 11 by the current potential of processed substrate 4 conductor plate behind, and make ion exposure on the surface of processed substrate 4.
In this example, adopted glass substrate as processed substrate 4, but the kind of employed processed substrate 4 is not limited to glass substrate.As mentioned above, even owing under 100 ℃ substrate temperature, also can form superior in quality film, so can adopt the substrate that forms by organic material.For example, can use vitrification point is substrate of the resinaes such as plastic base about 200 ℃ etc.According to device of the present invention, also can form silicon nitride film or amorphous silicon film, and carry out the making of TFT device the substrate of resinae etc.
In this example, the frequency as employed high frequency electric source 1 has adopted 13.56MHz, but the frequency of high frequency electric source 1 is not limited thereto.In the device of this example,, do not increase such baneful influence so under the low frequency below the 13.56MHz, can not produce the plasma damage that becomes problem usually owing on the surface of processed substrate 4, there is plasma 11 hardly.Therefore, also can use the following low frequency of 13.56MHz.But as lower frequency limit, 300KHz is suitable.Its reason is that the validity limit frequency that improves ion concentration by seizure ion between two electrode 2a, 2b is 300KHz.
In addition, even be commonly called VHF (Very HighFrequency: very high frequency(VHF)) also can use under Qu the high frequency more than the 13.56MHz.Under the situation of parallel plate-type device,, in large-scale plant, exist the problem that produces standing wave along with frequency improves, free space wavelength shortens.Here, be described in detail.High frequency, the form that distributes with in plasma (in detail, at isoionic surface element) exists.Therefore, the big or small degree that may exist as standing wave for example is 1/2 wavelength, isoionic size was about 1.5m when frequency was 100MHz, and then the generation of standing wave will make high frequency intensity become inhomogeneous.Therefore, the abnormal conditions of the film forming thickness attenuation at the position of the film forming thickness thickening at the position that generation high frequency intensity is strong, high frequency weak strength.
According to the present invention, the plasma portion little independent form of respectively doing for oneself, thereby on principle, just can not produce standing wave.Here, be described in detail.Under situation of the present invention, produce the plasma below several centimetres of the normal direction of the corresponding little plasma of many and electrode pattern, for example negative electrode 2a.In Fig. 2, Fig. 3 and Fig. 4, adjacent plasma portion looks and seems to interconnect, but in fact on positive electrode 2b by disjunction.Therefore, the propagation of high frequency consequently can not produced standing wave by the gap portion disjunction that waits the particle body of adjacency.So,, also can import the high frequency in VHF district even in large-scale plasma CVD apparatus.But as upper limiting frequency, 300MHz is suitable.Because 300MHz makes by catch electronics between two electrode 2a, 2b to improve the frequency that the effect of electron density reaches capacity, even can not change so frequency is brought up to this effect that is worth above electron density yet, on the contrary, the input of high frequency power but may cause a lot of difficulties.
Working of an invention form 2
Fig. 6 is a stereogram of schematically representing the plasma CVD apparatus of the invention process form 2, and Fig. 7 is a sectional drawing of schematically representing the plasma CVD apparatus of example 2.In addition, Fig. 8 is the partial enlarged drawing of Fig. 7.The limit is with reference to the plasma CVD apparatus of Fig. 6～Fig. 8 limit explanation example 2.In the following description, represent to have in fact inscape with the plasma CVD apparatus identical functions of example 1, and its explanation is omitted with identical reference marks.
The plasma CVD apparatus of the invention process form is on the concavity face this point at the plasma discharge face of negative electrode 2a, is that the plasma CVD apparatus of flat example 1 is different with the plasma discharge face of negative electrode 2a.
That is, as shown in Figure 8, the negative electrode 2a in the groove 18 has a pair of inclined plane that its lateral oblique upper is extended from the position near gas introduction port 6.In other words, the bottom of groove 18 constitutes from gas introduction port 6 and becomes big taper section gradually to the direction of processed substrate 4.This pair of angled face, the plasma discharge face of formation negative electrode 2a.
For example, in this example, as positive electrode 2b, preparing a plurality of section configurations is that rectangle, length are the aluminium bar of 300cm.As negative electrode 2a, preparing size is the aluminium sheet of 3mm for 110cm * 110cm, thickness.In addition, also preparing a plurality of section configurations is that right-angled triangle, length are the aluminium bar of 100cm.With section is that leg-of-mutton aluminium bar is fixed on the surface of aluminium sheet, make section be the vertical plane of leg-of-mutton aluminium bar and vertical plane that adjacent section is leg-of-mutton aluminium bar toward each other and the mutual almost parallel of each aluminium bar ground is extended.
In the space between the vertical plane of the triangular section aluminium bar that is clipped in adjacency, filling is as the aluminium oxide of insulant.Thus, be that the middle form of leg-of-mutton aluminium bar forms insulated part 3 between electrode to be clipped in section.With section is that rectangular aluminium bar is configured between electrode on the insulated part 3.According to this configuration, the section that positive electrode 2b can be used is that rectangular aluminium bar is leg-of-mutton aluminium bar electrical isolation with the aluminium sheet and the section that are used as negative electrode 2a.
In the direction of extending with positive electrode 2b roughly on the section of the direction of quadrature, the width d1 of insulated part 3 is 5mm between positive electrode 2b and electrode, the width d2 of negative electrode 2a is 10mm, the height d3 of insulated part 3 is 10mm between electrode, and insulated part 3 is spaced apart the 15mm spacing between each positive electrode 2b and electrode.In addition, the height d4 from the end of negative electrode 2a to positive electrode 2b is 5mm, and the section of negative electrode 2a is that the bottom width d5 of gable is 3mm.
High frequency voltage is applied on the aluminium sheet part of electrode base board.Therefore, aluminium sheet and section are leg-of-mutton aluminium bar, play a part negative electrode 2a, will be set at earthing potential by the aluminium bar of insulated part between electrode 3 and its insulation, and used as positive electrode 2b.
Make under the situation of silicon nitride film at the device of this example, film forming speed is 0.6nm (6 )/second, and uniformity is ± 3% in the film of thickness.Compare with example 1, the reason that film forming speed is accelerated, as described below.
In example 1, be used to make the Surface Vertical of insulated part 3 between the electrode that insulate between two electrode 2a, the 2b in the face of negative electrode 2a, so, behind insulated part 3 between plasma particle that produces on the surface of negative electrode 2a or atomic group particle impacting electrode, be easy to disappear.And under situation of the present invention, can make the surface of insulated part 3 between electrode and the inclined plane angulation of negative electrode 2a is the obtuse angle, preferably is roughly 180 °.Therefore, the probability that insulated part 3 backs disappear between the plasma particle that produces on the surface of negative electrode 2a or atomic group particle impacting electrode are lowered.In addition, because the section configuration of the plasma discharge face of negative electrode 2a is a spill, so also produce hollow cathode effect.Therefore, be concave shape by the plasma discharge face that makes negative electrode 2a, can keep the membranous disposal ability of improving when waiting other performances as device.
In example 1 and 2, the situation that plasma process device of the present invention is applied to plasma CVD apparatus is illustrated, but plasma process device of the present invention is not limited to plasma CVD apparatus.The present invention also can be applied to utilize plasma to carry out all plasma process devices that film forms the plasma treatment of processing etc., for example goes for dry etching device or soot blower.
For example, under the situation that is applied to the dry etching device,, adopt CF as the gas that imports process chamber 5 4, SF 6, Cl 2, HCl, BCl 3, O 2Deng etching gas.In general, in the dry etching device, in the etching action, not only use the atomic group that generates by plasma discharge, but also the processed face of processed substrate is carried out bombardment by ions.For example, at the back side of processed substrate 4 a bombardment by ions control is installed in addition and use electrode, and this electrode is connected with power supply and supplies with the current potential of stipulating, thereby can control bombardment by ions.
By adopting device of the present invention, can make gaseous dissociation expeditiously and improve etching speed, except that the plasma portion of disassociation usefulness, can also adjust bombardment by ions, so, make its controlled improving.
In example 1 and 2, positive electrode 2b is illustrated than the situation of the more approaching processed substrate 4 of negative electrode 2a, but also can makes negative electrode 2a than the more approaching processed substrate 4 of positive electrode 2b.In addition, also can make the current potential between positive electrode 2b and the negative electrode 2a just concern counter-rotating at any time.
In example 1 and 2, the situation that gas introduction port 6 is located at negative electrode 2a side is illustrated, but the position that is provided with of gas introduction port 6 is not limited thereto.For example, also gas introduction port 6 can be arranged to be located between plasma discharge generating unit 15 and the processed substrate 4.In this case, the surface direction of gas along processed substrate 4 imported in the process chamber 5 from gas introduction port 6.
Working of an invention form 3
As the electronic device of making of the plasma CVD apparatus of example 1 or 2, below, the actual organic electroluminescent device of making is shown.Fig. 9 is a sectional drawing of schematically representing organic electroluminescent device.
Organic electroluminescent shown in Figure 9 (below, abbreviate EL as) element, the structure that the negative electrode 23 that has the anode 26 that will be made of aluminium, organic hole transfer layer 25, organic luminous layer 24, is made of calcium, the transparency electrode 22 that is made of tin indium oxide stack gradually on processed substrate 4.As organic hole transfer layer 25, adopt diamine dielectric ((1,1 '-bis (4-di-p-tolylamino-phenyl) cyclohexane; TPD), as organic luminous layer 24, adopt oxine complex compound (tris (8-hydroxyquinolinato) aluminum (III); Alq3), and respectively form film with vacuum vapour deposition.
The organic EL of this example has transparent insulating film 21 as diaphragm at skin.Behind transparent insulating film 21 formation silicon nitride films (thickness 500nm (5000 )), can finish electronic device.Below, this electronic device is called device a.In addition, in the membrance casting condition of silicon nitride film, the temperature of processed substrate 4 is 80 ℃, and illustrated mistake is identical in other conditions and example 1 and 2.
As a comparative example 1, adopt Figure 33 and parallel plate-type device shown in Figure 34 press the same terms formation silicon nitride film.To have this silicon nitride film and be called device b as the electronic device of diaphragm.In addition, as a comparative example 2, made not forming diaphragm and covered recessed glass substrate that capping as an alternative uses on top and the electronic device after the sealing in nitrogen atmosphere.This electronic device is called device c.The structure of device c is the general up to now structure of using.
As a result of, in device a and device c, any structure is not in the early stage, all difference on the long-term characteristics of luminescence.Therefore,, need not to use capping glass, just can realize having and the electronic device of capping with the same excellent protection film of glass according to the present invention.This situation means electronic device of the present invention and uses capping to compare with the existing electronic device of glass to have higher productivity ratio.
On the other hand,, in the action test, on illuminating part, repeatedly produce non-luminous stain, present bad action for device b.Its reason is commonly considered as, and by the silicon nitride film that the parallel plate-type device is made, is unsuitable for as diaphragm, and the oxygen in the atmosphere has seen through this film.
In this example, the device that comprises organic membrane is shown.Because organic membrane will make the characteristic degradation of film in the heat treatment process more than 100 ℃, so have good membranous diaphragm even under near 100 ℃ temperature, also be preferably formed as during film forming.According to plasma process device of the present invention, as implementing shown in the form 1, even the temperature of processed substrate 4 near 100 ℃, also can form high-quality diaphragm, so the device of the application of the invention can be brought into play the advantage that it has.
As diaphragm, also to be easy to keep nitrogenous films such as good membranous silicon nitride film or silicon oxynitride film be effective even the temperature of processed substrate 4 is a low temperature.In nitrogenous film, when making the diaphragm characteristic degradation because of the structure of film is fine and close inadequately, the bonding of silicon, nitrogen and hydrogen in the film is replaced into the bonding of silicon and oxygen owing to the moisture in the atmosphere.Therefore, nitrogenous diaphragm has the membranous advantages of inspection such as can utilizing fourier transform infrared spectroscopy.Particularly, even owing in production process, also can monitor simply, so have the high advantage of productivity ratio.
In this example, show the device that comprises organic membrane, but other devices, for example solar cell or GaAs series electronic device etc. are not contained the electronic device of organic membrane, also can be with same film as diaphragm.
In the electronic device of this example, utilize the transparent insulating film 21 of the device formation of example 1 or 2 as diaphragm.But electronic device of the present invention is not limited to the device made from plasma process device of the present invention and manufacture method of the present invention.Contain the dielectric film of silicon and nitrogen and the hydrogen binding capacity in the dielectric film is 7 * 10 so long as on insulated substrate, form 21Cm -3More than, even then the device that obtains with the apparatus and method beyond the present invention is also included within the electronic device of the present invention.
In addition,, pay no attention to the film formation device and the film build method of its dielectric film, all be included in the electronic device of the present invention so long as in the use of device, in the film of the dielectric film that forms as skin, in fact do not produce the electronic device of oxygen key.
According to plasma process device of the present invention, can carry out film forming processing to processed substrate 4 with high quality and high gaseous dissociation efficient.For example, for making the active-drive LCD, must form the TFT portion that has adopted amorphous silicon film, silicon nitride film etc.When making with plasma CVD apparatus, in its manufacturing process, can not produce plasma damage, and can realize high gaseous dissociation efficient, thereby can carry out the film forming processing under the irrealizable parameter region (for example, substrate temperature is about 100 ℃) up to now.Therefore, can carry out TFT to the resinae substrate that has difficulties in the use up to now etc. makes.
Perhaps, in the field beyond the LCD, the light transform layer as the amorphous silicon solar cell can form amorphous silicon film with plasma CVD method equally.Plasma process device of the present invention even in the field of amorphous silicon solar cell, also has same effect.
Further, for the electronic device of organic electroluminescent device, polycrystalline silicon solar cell, GaAs class etc., also can be used as the device that forms as the transparent insulating film of outer protective film and use.Particularly, as the diaphragm of organic electroluminescent device, technological temperature must be below 100 ℃.According to device of the present invention, handle even in this temperature province, also still can carry out high-quality film forming.In addition, for polycrystalline silicon solar cell, even under lower technological temperature, also still can make and identical in the past diaphragm.Therefore, can guarantee the stability of device and the simplification of device maintenance.
In the operation of making the active-drive LCD, when the formation pattern to film carries out dry etching, by adopting plasma process device of the present invention, not only can realize high controlled to parameter, and can realize high gaseous dissociation efficient.In addition, adopting under the situation of soot blower, equally not only can realize high controlledly, and can realize high gaseous dissociation efficient.Both can both realize high gaseous dissociation efficient, therefore can expect to improve the disposal ability of device.
According to the present invention, can be implemented in the electronic device that skin has the high-quality diaphragm.Particularly, can form high-quality diaphragm being lower than under 100 ℃ the technological temperature.Therefore, the characteristic that can keep organic pleurodiaphragmatic in terspace to have.In addition, because need be with the top of capping, so can make device with high productivity ratio with the glass substrate cladding element.Therefore, can realize lighter slim organic electroluminescent device.
Working of an invention form 4
Figure 10 illustrates example 4 of the present invention.Figure 10 is the sectional drawing that illustrates behind plasma discharge generating unit 15 local the amplifications.
This example 4 forms crooked curved face part 31 downwards with the inclined plane in the groove in the example 2 18.In other words, the plasma discharge face of negative electrode 2a has the curved face part 31 of spill.In addition, by curved face part 31 being constituted the arc surface that is connected with the side of each adjacent insulated part 3, groove 18 is constituted the U font.
Therefore,, compare, can increase the basal area of groove 18 with the structure on the inclined plane with taper section of example 2 according to this example 4.In other words, can increase near the plasma area of negative electrode 2a.Consequently, can increase the gas burst size and the gas lysis efficiency of per unit gas flow, so, can make rate of film build and membranous being improved.
, when the gas flow that imports from gas introduction port 6 is subjected to blocking, in this retardance zone, be easy to produce powder.Different therewith, in this example, because the surface of the negative electrode 2a around the gas introduction port 6 forms the curved surface of spill, so, gas is flowed glibly, thereby can suppress the generation of powder.Consequently, can suppress powder and sneak in the film, thereby can make membranous raising.
Here, for estimating the membranous and rate of film build of formed film, in table 2, list residual stress to the SiN film and be the value after membrane stress and rate of etch are carried out practical measurement.
Table 2
Membrane stress (Mpa) Rate of etch (/s)
Embodiment 1 ????563 ????271
Embodiment 2 ????473 ????256
With the structure on the taper inclined plane of above-mentioned example 2 shown in Figure 8 as embodiment 1, and with the structure with curved face part 31 of example shown in Figure 10 4 as embodiment 2.Then, embodiment 1 and 2 has been carried out the mensuration of membrane stress and rate of etch.For membrane stress, on silicon chip, form SiN (silicon nitride) film, and measured the angularity of the substrate of these film forming front and back with well-known stress determination device.For rate of etch, utilize BHF (buffered hydrofluoric acid) that is diluted to 1/100 and the rate of etch (during normal temperature) of having measured the SiN on the silicon chip with well-known step discrepancy in elevation determinator.
At this moment, the basal area of the groove 18 of embodiment 2 is 2 times of embodiment 1.In addition, membrane stress, embodiment 2 is 1 approximately littler by 16% than embodiment, rate of etch is approximately little by 5.5%.That is,, membrane stress is lowered, rate of etch is reduced, thereby make film more fine and close by the plasma discharge face being formed the curved surface of spill.
Working of an invention form 5
Figure 11 illustrates example 5 of the present invention.Figure 11 is the figure suitable with Figure 10 that illustrates behind plasma discharge generating unit 15 local the amplifications.
This example, different with above-mentioned example 2, make groove 18 become darker by increasing ditch depth to the ratio of furrow width.That is, the degree of depth of groove 18 is greater than furrow width.Further, the side of groove 18 and bottom surface are connected continuously by curved face part 31, according to this configuration, also can obtain the effect identical with above-mentioned example 4.In addition, in this example, compare with above-mentioned example 4, the basal area of groove 18 is bigger, so, the burst size and the lysis efficiency of gas can be improved, thereby membranous further raising can be made.
Working of an invention form 6
Figure 12 illustrates example 6 of the present invention.Figure 12 is the figure suitable with Figure 10 that illustrates behind plasma discharge generating unit 15 local the amplifications.
This example, different with above-mentioned example 4, not only will also constitute curved surface in the groove 18 but also with the surface of positive electrode 2b.In other words, the plasma discharge face of negative electrode 2a and the plasma discharge face of positive electrode 2b constitute the part of continuous curve surface.Above-mentioned continuous curved surface is made of the convex surface portion 33 of the concave curvatures portion 31 of negative electrode 2a, the curved face part 32 that forms in the side of insulated part 3, positive electrode 2b.In other words, in the plasma discharge generating unit 15 towards the surface of processed substrate 4 one sides, form continuous wavy curved surface.
In above-mentioned example 4, though the simple shape of positive electrode 2b and insulated part 3 thereby be easy to form is concentrated thereby might be produced paradoxical discharge at seamed edge portion (bight) electric field of positive electrode 2b.Different therewith, in this example, positive electrode 2b is made the curved surface shape, concentrate so can prevent electric field, thereby can suppress to produce powder because of paradoxical discharge.Consequently, can make membranous further raising.
Working of an invention form 7
Figure 13 illustrates example 7 of the present invention.Figure 13 is the figure suitable with Figure 10 that illustrates behind plasma discharge generating unit 15 local the amplifications.
This example, different with above-mentioned example 2, be provided with recess 35 in the formation position of gas introduction port 6.In other words, on the plasma discharge face of negative electrode 2a, in groove 18, forming a plurality of recess 35 with lining up into row, forming gas introduction port 6 in the bottom of recess 35 along the groove direction.
Therefore,, can produce hollow cathode effect by each recess 35 according to this example, so, the amount of electrons that flies out from negative electrode 2a is increased, thereby can further promote the cracking of gas.That is, the burst size and the lysis efficiency of per unit gas flow can be increased, thereby rate of film build and membranous being improved can be made.Further, be located at the bottom of recess 35 owing to will spray the gas introduction port 6 of gas, so in recess 35, also just unwanted film need not have been adhered to.
Working of an invention form 8
Figure 14 illustrates example 8 of the present invention.Figure 14 is the figure suitable with Figure 10 that illustrates behind plasma discharge generating unit 15 local the amplifications.This example, different with above-mentioned example 2, the mode with same with example 7 is provided with recess 35 in the formation position of gas introduction port 6.
According to this configuration, can obtain the effect identical with above-mentioned example 7.In addition, owing to can increase plasma area by the basal area that increases groove 18, so can make rate of film build and membranous further raising.
Working of an invention form 9
Figure 15 illustrates example 9 of the present invention.Figure 15 is the stereogram that illustrates after plasma discharge generating unit 15 is amplified.
This example, different with above-mentioned example 2, formed a plurality of recess 35 on the inclined plane in the groove 18 of negative electrode 2a.Recess 35 is arranged side by side respectively along the Width and the ditch length direction of groove 18.
Therefore,, make roughly the negative electrode 2a that forms by the V font produce hollow cathode effect as a whole, also produce hollow cathode effects simultaneously by each recess 35 of the plasma discharge face of negative electrode 2a according to this example, so, can radiate more electronics.Consequently, can make the gas cracking effectively, thereby can make membranous raising.
Simultaneously, in the zone of plasma discharge face specified altitude, forming is not the negative electrode covering part of plasma area.Owing in the negative electrode covering part, pass through with high speed from gas introduction port 6 gas supplied, so also can not block gas flow by plasma area even on the plasma discharge face, formed a plurality of recess 35.
Working of an invention form 10
Figure 16 illustrates example 10 of the present invention.Figure 16 is the stereogram that illustrates after plasma discharge generating unit 15 is amplified.
This example, different with the plasma discharge face of negative electrode 2a in the above-mentioned example 9, not that recess 35 is set, but carried out sandblast processing.That is, the plasma discharge face of negative electrode 2a, surface roughness is bigger, from microcosmic, is forming many sags and crests on the plasma discharge face.Therefore, carry out sandblast processing, can produce hollow cathode effect, thereby can make membranous raising by plasma discharge face to negative electrode 2a.
Working of an invention form 11
Figure 17 and Figure 18 illustrate example 11 of the present invention.Figure 17 is the stereogram that illustrates after plasma discharge generating unit 15 is amplified, and Figure 18 is the vertical view of expression plasma discharge generating unit 15.
This example to negative electrode 2a, is arranged along the direction of ditch in the bottom of groove 18 between adjacent insulated part 3 and is provided with a plurality of openings towards by the recess 37 of processed substrate 4.In other words, this example, different with above-mentioned example 2, be provided with the separating part 38 of separating groove 18 in accordance with regulations at interval along the direction of ditch.
That is, recess 37, opening shape are quadrangle, are made of the bottom surface of groove 18, the pair of angled face of negative electrode 2a, a pair of division surface of separating part 38.The division surface of separating part 38 is so that the bottom of separating part 38 tilts to the mode of the both sides of ditch direction expansion.Therefore, the open section of recess 37 is more little more downwards.
In addition, be located at a plurality of recesses 37 between each insulated part 3, as shown in figure 18, when the normal direction of processed substrate 4 is looked by staggered configuration.In recess 37, a plurality of gas introduction ports 6 along the direction of ditch is arranged are provided with on the bottom of the groove 18 in recess 37 and the division surface of separating part 38 continuously.
Therefore,, can increase the surface area of negative electrode 2a, so can improve the lysis efficiency and the rate of film build of gas according to this example.In addition, owing to make recess 37, can make the quality of the film that on processed substrate 4, forms become even by staggered configuration.The shape of recess is not limited to quadrangle, for example, also can be made of polygonals such as octangles.
Working of an invention form 12
Figure 19 and Figure 20 illustrate example 12 of the present invention.Figure 19 is the stereogram that illustrates after plasma discharge generating unit 15 is amplified, and Figure 20 is the vertical view of expression plasma discharge generating unit 15.
This example, different with above-mentioned example 11, the opening shape of recess 37 is changed to circle.That is, in the bottom of groove 18, along the direction of ditch arrange be provided with a plurality of Yan ?the recess 37 of shape.Between each recess 37 of adjacency, small interval is being set.In addition, in the bottom of each recess 37, for example arrange 2 gas introduction ports 6 of formation along the direction of ditch.
As mentioned above, even the opening shape of recess 37 is changed to circle, also can obtain the effect identical with above-mentioned example 11.In addition, the inside of recess 37 is made of curved surface, so, the gas that imports from gas introduction port 6 is flowed glibly,
In addition, the opening shape of recess 37 is not limited to positive circle, also can be circles such as ellipse.In addition, also a plurality of recesses 37 can be set on the ditch cross direction to groove 18.
Working of an invention form 13
Figure 21 and Figure 22 illustrate example 13 of the present invention.Figure 21 is the stereogram of expression plasma discharge generating unit 15 and processed substrate 4.Figure 22 is the sectional drawing that illustrates behind plasma discharge generating unit 15 local the amplifications,
This example is with above-mentioned example 2 differences, is located at each the negative electrode 2a between the adjacent insulated part 3, in the mutual electrical isolation in the left and right sides of insulated part 3.Promptly, as Figure 21 and shown in Figure 22, plasma discharge generating unit 15, by the insulation board 40 relative with processed substrate 4, insulated part 3 be set by strip on the insulation board 40, be located at negative electrode 2a between adjacent each insulated part 3, the positive electrode 2b that is located at the upper end of each insulated part 3 constitutes.
Therefore, the same with above-mentioned example 2 in this example as shown in figure 22, groove 18 is made of 2 sides of insulating barrier 3 that faces with each other and positive electrode 2b and the upper surface of negative electrode 2a.Gas introduction port 6 forms with the form that connects negative electrode 2a and insulation board 40.In addition, on negative electrode 2a, has the plasma discharge face of the inclination identical with above-mentioned example 2.According to this configuration, can obtain the effect identical with above-mentioned example 2.
Working of an invention form 14
Figure 23 illustrates example 14 of the present invention.Figure 23 is the sectional drawing that illustrates behind expression plasma discharge generating unit 15 local the amplifications.
This example is with above-mentioned example 13 differences, and the plasma discharge face of negative electrode 2a as example 1, is made of the plane parallel with processed substrate 4.That is, each negative electrode 2a is in the mutual electrical isolation in the left and right sides of insulated part 3.According to this configuration, can obtain the effect identical with above-mentioned example 1.
Working of an invention form 15
Figure 24 and Figure 25 illustrate example 15 of the present invention.Figure 24 and Figure 25 are the sectional drawings that illustrates behind plasma discharge generating unit 15 local the amplifications.
In this example, different with above-mentioned example 13 and 14, insulation board 40 is not set.That is, Figure 24 is equivalent to the upper portion of the plasma discharge generating unit 15 of above-mentioned example 13 shown in Figure 22.On the other hand, Figure 25 is equivalent to the upper portion of the plasma discharge generating unit 15 of above-mentioned example 14 shown in Figure 23.According to this configuration, also can obtain and above-mentioned example 1 or 2 identical effects.
Working of an invention form 16
Figure 26 and Figure 27 illustrate example 16 of the present invention.Figure 26 and Figure 27 are the sectional drawings that illustrates after amplifying plasma discharge generating unit 15 is local, the discharge path when Figure 26 represents that gas pressure is higher, and the discharge path of Figure 27 when representing that gas pressure is low.
This example, different with above-mentioned example 2 on the collocation point of gas introduction port 6.That is, on the direction that the length direction with the insulated part 3 of strip intersects, arrange a plurality of gas introduction ports 6 are being set.A plurality of gas introduction ports 6 as shown in figure 26, are preferably on the direction (ditch cross direction in other words) with the length direction quadrature of the insulated part 3 of strip being spaced in accordance with regulations.One group of gas introduction port 6 that these are arranged along the ditch cross direction, interval in accordance with regulations is along the many groups of ditch length direction configuration.Therefore, when the normal direction of processed substrate 4 was looked, gas introduction port 6 was pressed the configuration of ranks shape in the bottom of groove 18.
In addition, be located at the gas introduction port 6 on each inclined plane, constitute and make it with direction parallel to each other ejection gas.In other words, each gas introduction port 6 constitutes by the normal direction break-through negative electrode 2a along processed substrate 4.
, when with gas introduction port 6 in the central authorities of groove 18 when the ditch length direction is lined up 1 row and is formed, the air-flow on the ditch cross direction distributes, and is that laminar flow thereby speed are very fast in the central authorities of ditch, but the both sides of ditch cross direction are for turbulent flow thereby might become slower.Thereby the turbulent flow that exists this air-flow causes the problem of the generation of powder.
Different therewith, in this example, along ditch cross direction interval in accordance with regulations a plurality of gas introduction ports 6 that spray gas with direction parallel to each other are set, also in accordance with regulations interval is provided with a plurality of gas introduction ports 6 along the ditch length direction simultaneously, so the air-flow that can make the inside of groove 18 is uniform laminar flow.That is,, can reduce the generation of powder by the generation that suppresses the turbulent flow in the plasma area, so can make membranous being improved according to this example.
Further, shown in this example, a plurality of gas introduction ports 6 are set, can increase the sum of gas introduction port 6 by Width at groove 18.Therefore, when the gas with certain flow imports in the process chamber 5, can reduce the inflow velocity of gas, so, the gas hold-up time that can prolong the plasma area in the groove 18.In addition, can also make in mode parallel to each other from the gas of a plurality of gas introduction ports 6 ejections respectively along the path flow of plasma discharge.Consequently, can promote the disassociation and the cracking of gas well, so can make membranous being improved.
Working of an invention form 17
Figure 28 is a sectional drawing of schematically representing the plasma CVD apparatus of the invention process form 17, and the limit describes with reference to the plasma CVD apparatus of Figure 28 limit to example 17.
In this example 17, the inclined plane in the groove in the above-mentioned example 16 18 is formed crooked curved face part 31 downwards.In other words, the plasma discharge face of negative electrode 2a has the curved face part 31 of spill.In addition, by curved face part 31 being constituted the arc surface that is connected with each side of adjacent insulated part 3, groove 18 is constituted the U font.
Therefore,, compare, can increase the basal area of groove 18 with the structure on the inclined plane with taper section of above-mentioned example 16 according to this example.In other words, can increase near the plasma area of negative electrode 2a.Consequently, can increase the gas burst size and the gas lysis efficiency of per unit gas flow, so, can make rate of film build and membranous being improved.
, when the gas flow that imports from gas introduction port 6 is subjected to blocking, in this retardance zone, be easy to produce powder.Different therewith, in this example, because the surface of the negative electrode 2a around the gas introduction port 6 forms the curved surface of spill, so, gas is flowed glibly, thereby can suppress the generation of powder.Consequently, can suppress powder and sneak in the film, thereby can make membranous raising.
Here, for estimating the membranous and rate of film build of formed film, in table 3, list residual stress to the SiN film and be the value after membrane stress and rate of etch are carried out practical measurement.
Table 3
Membrane stress (Mpa) Rate of etch (/s)
Embodiment 3 ????473 ????256
Embodiment 4 ????436 ????162
Will be in the plasma discharge generating unit 15 of Figure 28 line up structure that 1 row ground forms gas introduction port 6 as embodiment 3 along the ditch length direction in the central authorities of groove 18, and with the structure with curved face part 31 of this example shown in Figure 28 as embodiment 4.Then, embodiment 3 and 4 has been carried out the mensuration of membrane stress and rate of etch.For membrane stress, on silicon chip, form SiN (silicon nitride) film, and measured the angularity of the substrate of these film forming front and back with well-known stress determination device.For rate of etch, utilize BHF (buffered hydrofluoric acid) that is diluted to 1/100 and the rate of etch (during normal temperature) of having measured the SiN on the silicon chip with well-known step discrepancy in elevation determinator.
At this moment, the total aperture area of a plurality of gas introduction ports 6 of embodiment 4 is 5 times of embodiment 3.In addition, membrane stress, embodiment 4 is 3 approximately littler by 7.8% than embodiment, rate of etch is approximately little by 3.7%.That is,, membrane stress is lowered, rate of etch is reduced, thereby make film more fine and close by the plasma discharge face being formed the curved surface of spill.
Working of an invention form 18
Figure 29 is a sectional drawing of schematically representing the plasma CVD apparatus of the invention process form 18, and the limit describes with reference to the plasma CVD apparatus of Figure 29 limit to example 18.
This example, different with above-mentioned example 17, make groove 18 become darker by increasing ditch depth to the ratio of furrow width.That is, the degree of depth of groove 18 is greater than furrow width.Further, the side of groove 18 and bottom surface are connected continuously by curved face part 31, according to this configuration, also can obtain the effect identical with above-mentioned example 17.In addition, in this example, compare with above-mentioned example 17, the basal area of groove 18 is bigger, so, the burst size and the lysis efficiency of gas can be improved, thereby membranous further raising can be made.
Working of an invention form 19
Figure 30 illustrates example 19 of the present invention.Figure 30 is the sectional drawing that illustrates behind plasma discharge generating unit 15 local the amplifications.
This example, different with above-mentioned example 17, not only will also constitute curved surface in the groove 18 but also with the surface of positive electrode 2b.In other words, the plasma discharge face of negative electrode 2a and the plasma discharge face of positive electrode 2b constitute the part of continuous curve surface.Above-mentioned continuous curved surface is made of the convex surface portion 33 of the concave curvatures portion 31 of negative electrode 2a, the curved face part 32 that forms in the side of insulated part 3, positive electrode 2b.In other words, in the plasma discharge generating unit 15 towards the surface of processed substrate 4 one sides, form continuous wavy curved surface.
In above-mentioned example 17, though the simple shape of positive electrode 2b and insulated part 3 thereby be easy to form is concentrated thereby might be produced paradoxical discharge at seamed edge portion (bight) electric field of positive electrode 2b.Different therewith, in this example, positive electrode 2b is made the curved surface shape, concentrate so can prevent electric field, thereby can suppress to produce powder because of paradoxical discharge.Consequently, can make membranous further raising.
Working of an invention form 20
Figure 31 is a stereogram of schematically representing the plasma CVD apparatus of the invention process form 20.In Figure 31,, the diagram of the hatching of negative electrode 2a is omitted for ease of explanation.The limit describes with reference to the plasma CVD apparatus of Figure 31 limit to example 20.
This example, different with above-mentioned example 17, make the gas emission direction difference of gas introduction port 6.That is, each gas introduction port 6 constitutes gas is sprayed obliquely with respect to the normal direction of processed substrate 4.As shown in figure 31, on the curved face part 31 in the left side of groove 18,7 row gas introduction ports 6 for example are set, form gas is sprayed obliquely to the upper right side.On the other hand, the same with the curved face part in left side on the curved face part 31 on right side, 7 row gas introduction ports 6 for example are set, form gas is sprayed obliquely to the upper left side.In addition,, for example arrange formation 3 row gas introduction ports 6, and the normal direction of gas along processed substrate 4 sprayed by these gas introduction ports 6 along the ditch length direction in the bottom of groove 18.In addition, each gas introduction port 6, on each zone of the bottom of the curved face part 31 in left side, right side curved face part 31, groove 18, ejection in a parallel manner separately.
Therefore, according to this example, be incline direction owing to make the emission direction of gas, thus can prolong gas distance by plasma area in groove 18, thereby can promote the disassociation and the cracking of gas, so can make membranous being improved.
Working of an invention form 21
Figure 32 illustrates example 21 of the present invention.Figure 32 is the sectional drawing that illustrates behind plasma discharge generating unit 15 local the amplifications.
This example, different with above-mentioned example 16, changed the gas emission direction of gas introduction port 6.That is, each gas introduction port 6, on the ditch cross direction of groove 18, arrange a plurality of, and constitute make gas to the vertical direction ejection in inclined plane as the plasma discharge face of negative electrode 2a.
In groove 18,, in this example, only on an inclined plane gas introduction port 6 is set therein though respectively have 2 inclined planes.Further, the same with above-mentioned example 1, also gas introduction port 6 is set in the bottom of groove 18.These gas introduction ports 6 also are that alignment arrangements is a plurality of respectively along the ditch length direction.
, the path of plasma discharge, with the direction of the plasma discharge face quadrature of negative electrode 2a on form.Therewith accordingly, according to this example, make the emission direction and the plasma discharge face quadrature of gas, so gas can be imported along discharge path.Therefore, can carry out the cracking and the disassociation of gas expeditiously.
In addition, owing to only on the inclined plane in 2 inclined planes of each groove 18 gas introduction port 6 is set, so compare the generation of the turbulent flow that can suppress air-flow with situation about on 2 inclined planes, all being provided with.
In addition, in this example, make groove 18, but also can be other shape for to have the shape on 2 inclined planes.For example, also can constitute groove 18 by curved face part 31 as shown in Figure 6, and along the ditch cross direction a plurality of gas introduction ports 6 are set, the gas emission direction that makes each gas introduction port 6 simultaneously is the direction vertical with curved face part 31.
As mentioned above, the present invention, can be effectively applied to have the plasma process device, electronic device and the manufacture method thereof that between the 1st electrode and the 2nd electrode, produce the plasma discharge portion of plasma discharge, even be particularly useful under the reduction process temperature, also will making the occasion of membranous raising.

Claims (30)

1. plasma process device, this plasma processing unit (plant) is implemented plasma treatment on processed substrate, be characterised in that:
Possess
In inner mounting the process chamber of above-mentioned processed substrate;
In above-mentioned process chamber, import the gas introduction port of gas;
Be arranged on the plasma discharge generating unit in the above-mentioned process chamber,
The 2nd electrode that above-mentioned plasma discharge generating unit has the 1st electrode and is provided with than the more approaching above-mentioned processed substrate of above-mentioned the 1st electrode,
Above-mentioned the 1st electrode and above-mentioned the 2nd electrode play has only the effect as the plasma discharge face of the face that can discern from the normal direction of above-mentioned processed substrate.
2. plasma process device, this plasma processing unit (plant) is implemented plasma treatment on processed substrate, be characterised in that:
Possess
In inner mounting the process chamber of above-mentioned processed substrate;
In above-mentioned process chamber, import the gas introduction port of gas;
Be arranged on the plasma discharge generating unit in the above-mentioned process chamber,
Above-mentioned plasma discharge generating unit has the 1st electrode, is formed on the insulating barrier on the part of electrode surface of above-mentioned the 1st electrode and is formed on the 2nd electrode on the above-mentioned insulating barrier.
3. plasma process device according to claim 1 and 2 is characterised in that:
The above-mentioned gas introducing port is arranged on above-mentioned the 1st electrode one side.
4. plasma process device according to claim 1 and 2 is characterised in that:
The plasma discharge face of above-mentioned the 1st electrode is a concave.
5. plasma process device according to claim 1 and 2 is characterised in that:
The area of the plasma discharge face of above-mentioned the 1st electrode is bigger than the area of the plasma discharge face of above-mentioned the 2nd electrode.
6. plasma process device according to claim 1 and 2 is characterised in that:
Above-mentioned plasma discharge generating unit has the plasma discharge face district of a plurality of above-mentioned the 1st electrodes and the plasma discharge face district of above-mentioned the 2nd electrode respectively.
7. plasma process device according to claim 1 and 2 is characterised in that:
Direction along a face of above-mentioned processed substrate alternately forms the plasma discharge face district of a plurality of above-mentioned the 1st electrodes and the plasma discharge face district of above-mentioned the 2nd electrode, and the distance between above-mentioned the 2nd electrode and the above-mentioned processed substrate is more than the interelectrode distance of above-mentioned the 2nd electrode that adjoins each other.
8. plasma process device according to claim 1 and 2 is characterised in that:
Also have the power supply that applies electric energy on above-mentioned the 1st electrode and above-mentioned the 2nd electrode, the frequency of above-mentioned power supply is below the above 300MHz of 300kHz.
9. the manufacture method of an electronic device, this method are used has possessed in inner mounting the process chamber of processed substrate; In above-mentioned process chamber, import the gas introduction port of gas; Be arranged on the plasma process device of the plasma discharge generating unit in the above-mentioned process chamber, make electronic device, be characterised in that:
Comprise
Technology at the above-mentioned processed substrate of the inside of above-mentioned process chamber mounting;
In mounting in the above-mentioned process chamber of above-mentioned processed substrate, import the technology of above-mentioned gas from the above-mentioned gas introducing port;
By above-mentioned plasma discharge generating unit generation plasma discharge, implement the technology of plasma treatment on the surface of above-mentioned processed substrate,
Discharge path along above-mentioned plasma discharge imports above-mentioned gas.
10. the manufacture method of an electronic device, this method use the plasma treatment appts of claim 1 to make electronic device, are characterised in that:
Comprise
Technology at the above-mentioned processed substrate of the inside of above-mentioned process chamber mounting;
In mounting in the above-mentioned process chamber of above-mentioned processed substrate, import the technology of above-mentioned gas from the above-mentioned gas introducing port;
By above-mentioned plasma discharge generating unit generation plasma discharge, implement the technology of plasma treatment on the surface of above-mentioned processed substrate.
11. an electronic device, this electronic device on insulated substrate film forming dielectric film, be characterised in that:
Above-mentioned dielectric film comprises silicon, nitrogen and hydrogen, and the hydrogen binding capacity in the above-mentioned dielectric film is 7 * 10 21Cm -3More than.
12. electronic device according to claim 11 is characterised in that:
Oxygen binding capacity in the above-mentioned dielectric film comes down to 0.
13. electronic device according to claim 11 is characterised in that:
Above-mentioned dielectric film forms skin.
14. electronic device according to claim 11 is characterised in that:
Above-mentioned insulated substrate is formed by organic material.
15. electronic device according to claim 11 is characterised in that:
Can also have organic layer.
16. plasma process device according to claim 1 and 2 is characterised in that:
The plasma discharge mask of above-mentioned the 1st electrode has the curvature portion of spill.
17. plasma process device according to claim 16 is characterised in that:
The plasma discharge face of above-mentioned the 1st electrode and the plasma discharge face of above-mentioned the 2nd electrode constitute the part of continuous curve surface.
18. plasma process device according to claim 1 and 2 is characterised in that:
On the plasma discharge face of above-mentioned the 1st electrode, form a plurality of recess.
19. plasma process device according to claim 18 is characterised in that:
Gas introduction port is formed on the bottom at the above-mentioned recess of at least a portion.
20. plasma process device according to claim 1 and 2 is characterised in that:
The plasma discharge face of above-mentioned the 1st electrode is processed in sandblast.
21. plasma process device according to claim 1 and 2 is characterised in that:
A plurality of recesses towards processed base openings are being set on above-mentioned the 1st electrode.
22. plasma process device according to claim 21 is characterised in that:
The opening shape of above-mentioned recess is a quadrangle.
23. plasma process device according to claim 21 is characterised in that:
The opening shape of above-mentioned recess is circular.
24. a plasma process device, this plasma processing unit (plant) has possessed in inner mounting the process chamber of processed substrate; Import the gas introduction port of gas in the inside of above-mentioned process chamber; Be arranged on the inside of above-mentioned process chamber, on above-mentioned processed substrate, implement the plasma discharge generating unit of plasma treatment, be characterised in that:
Above-mentioned plasma discharge generating unit possesses a plurality of insulated parts that are the extension of strip ground along the direction parallel with above-mentioned processed substrate; At least the 1st electrode that between the above-mentioned insulated part that adjoins each other, is provided with; The 2nd electrode that is provided with state in the end of above-mentioned processed substrate one side of above-mentioned each insulated part with above-mentioned the 1st electrode separation.
25. plasma process device according to claim 24 is characterised in that:
Each the 1st electrode that is provided with between above-mentioned each insulated part is separated from each other.
26. plasma process device according to claim 24 is characterised in that:
In above-mentioned the 1st electrode, form a plurality of gas introduction ports,
The direction of intersecting along the length direction for the insulated part of above-mentioned strip is arranged above-mentioned a plurality of gas introduction port is set.
27. plasma process device according to claim 26 is characterised in that:
Above-mentioned a plurality of gas introduction port is along arranging with the direction of the length direction quadrature of above-mentioned insulated part.
28. plasma process device according to claim 26 is characterised in that:
Above-mentioned each gas introduction port constitutes along the direction blow gas that is parallel to each other.
29. plasma process device according to claim 26 is characterised in that:
Above-mentioned each gas introduction port constitutes along the direction blow gas vertical with the plasma discharge face of the 1st electrode.
30. plasma process device according to claim 26 is characterised in that:
Above-mentioned each gas introduction port constitutes the direction blow gas for the normal direction inclination of processed substrate.
CNB2003101013852A 2002-10-16 2003-10-16 Semiconductor device and its manufacturing method and plasma processing device Expired - Fee Related CN1293608C (en)

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