JP2001308078A - Organic matter removing method, semiconductor device manufacturing method, organic matter removing apparatus and system - Google Patents

Abstract

(57) Abstract: A resist layer is removed from a substrate so as to suppress corrosion of the substrate exposed from the resist layer. SOLUTION: A container 1 made of stainless steel or the like for defining a reaction chamber, an exhaust port 2 for exhausting the inside of the container 1, and a substrate 3 attached to a supporting means for supporting a semiconductor substrate and the like are heated. Heater 4, a gas introduction pipe 5 for introducing gas into the container 1, a dielectric window 6 for transmitting high-frequency power and isolating the inside and outside of the container, and a high-frequency power supply for supplying high-frequency power such as microwaves. Vessel 7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a semiconductor device, an organic substance removing method and an organic substance removing apparatus and system used for the method, and more particularly, to a method for removing a resist layer having an ion-implanted region. It is about.

[0002]

2. Description of the Related Art Conventionally, in order to form a device on a semiconductor substrate, a step of selectively etching an oxide film or the like formed on the semiconductor substrate or locally ion-implanting a substance such as phosphorus, arsenic, or boron. There is. In these steps, a photoresist layer made of an organic substance such as a photosensitive resin is used as a mask material.

[0003] When the selective etching is completed, for example, the photoresist layer becomes unnecessary and needs to be removed. Therefore, when the photoresist layer is made of an organic substance, the photoresist layer is oxidized or incinerated by an oxidizing action and removed by a dry process using oxygen plasma, oxygen radicals, ozone, or the like.

According to this method, for example, when oxygen gas is discharged or oxygen gas is irradiated with ultraviolet rays, activated oxygen is obtained and the resist layer is exposed to the oxygen. It utilizes the principle of becoming a gas such as water vapor, carbon dioxide or carbon monoxide, and is called ashing or the like.

However, when performing local ion implantation,
When removing the photoresist layer used as a mask material, the implanted ions alter and harden the vicinity of the surface of the photoresist layer, so that the photoresist layer is not easily oxidized. Took a long time to remove.

As a specific example, the reason why the implanted ions deteriorate the vicinity of the surface of the photoresist layer is that of Nuclear.
As described in Instruments and Methods, B39, pp. 809-812, when phosphorus is injected into a resist layer based on cresol novolak resin, for example, a phosphorus atom is bonded to a phenol ring in the main chain. And cross-linking that progresses through substitution with a methylene group.

When the deteriorated photoresist layer is heated to a normal ashing temperature of 150 ° C. to 250 ° C., vapor of an organic solvent is generated in a portion of the photoresist layer which is not deteriorated by ions, and This may cause so-called popping, which becomes particles on large flakes near the surface of the photoresist layer and scatters,
It is known that popping contaminates a semiconductor substrate.

Further, since the implanted ions are hardly volatilized by the oxidizing plasma and serve as a stable oxide generation source, an oxide is generated after the photoresist layer is ashed and removed by an active species such as oxygen. This oxide may remain on the semiconductor substrate. It is necessary to remove the remaining oxide from the semiconductor substrate, and therefore, it is necessary to remove the oxide with a cleaning liquid and further dry the semiconductor substrate.

The photoresist layer whose surface has been altered by ion implantation is generally ashed by oxygen plasma to which a fluorocarbon gas represented by CF ₄ is added.
The active species of fluorine remove the ionic species by converting them into volatile compounds. However, at this time, a portion of the semiconductor substrate where the photoresist layer is not formed, such as an opening of the photoresist layer, may be corroded due to prolonged exposure to an active species of fluorine. It is not preferable to use it in recent manufacturing processes for high-definition semiconductor devices that require more precise processing.

[0010] For this reason, Japanese Journal of Applied
Physics, Vol. 28, No. 10, pp. 2130-2136,
For example, using hydrogen plasma or water vapor plasma RIE (Reactive Ion Etching) to reduce and remove the deteriorated layer on the photoresist layer surface with active species of hydrogen that does not corrode the underlayer, and exist under the deteriorated portion. The part that has not been transformed is down-flowed using oxygen plasma.
A two-stage treatment method has been proposed in which the ash is removed by ashing or the like.

Japanese Unexamined Patent Publication No. 5-275326 discloses, for example, a method in which a deteriorated portion is incinerated and removed by plasma obtained by adding a fluorine-based gas having a function of removing implanted ion species to oxygen. A two-stage ashing method of ashing an unreacted resist layer portion with oxygen plasma is described. On the other hand, JP 200
JP-A No. 0-12521 describes an ashing method in which ashing is performed by plasma of a mixed gas of a fluorine-based gas, an oxygen gas, and a hydrogen gas.

[0012]

[Problems to be solved by the invention] However, Japanese Jou
rnal of Applied Physics, Vol. 28, No. 10, pp. 2130
In the ashing described in Nos. 1 to 2136, the processing speed of the ashing by the active species of hydrogen is slow, so that the processing efficiency may be reduced.

In the ashing described in Japanese Patent Application Laid-Open No. 5-275326, a portion of the semiconductor substrate on which the photoresist layer is not formed is exposed to a fluorine compound gas or a fluorine compound gas while the altered portion is ashed and removed. Since it is corroded by active species, it is not preferable to use it in a recent high-definition semiconductor device manufacturing process that requires more precise processing.

Furthermore, in the ashing described in Japanese Patent Application Laid-Open No. 2000-12521, the time of exposure to a fluorine compound gas or its active species becomes long, and the problem of corrosion cannot be sufficiently solved.

Accordingly, the present invention provides a method of removing a resist layer, a method of removing an organic substance, a method of manufacturing a semiconductor device, and a method of removing a resist layer from a substrate by suppressing corrosion of the substrate exposed from the resist layer. It is an object to provide a layer removing device.

[0016]

The gist of the present invention is to provide a method for removing an organic substance having an ion-implanted region from a substrate using at least a plasma of an oxygen-containing gas. A first step of introducing a hydrogen-containing gas and a fluorine-containing gas into a reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma process; and introducing an oxygen-containing gas without introducing a fluorine-containing gas. A second step of introducing a gas into the reaction chamber, generating a plasma of the gas introduced into the reaction chamber, and performing a plasma treatment.

Another gist of the present invention is a method for removing an organic substance having an ion-implanted region from a substrate using at least a plasma of an oxygen-containing gas. A first step of introducing a fluorine-containing gas into a reaction chamber, generating a plasma of the gas introduced into the reaction chamber, and performing a plasma treatment, so that the concentration of the fluorine-containing gas becomes 0.01% by volume or less. A second step of introducing a fluorine-containing gas and an oxygen-containing gas into a reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment.

Another gist of the present invention is a method of removing an organic substance having an ion-implanted region from a substrate using at least a plasma of an oxygen-containing gas. A first step of introducing a fluorine-containing gas into the reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment; and a step of controlling the concentration of the fluorine-containing gas by the fluorine introduced in the first step. A second step of introducing a fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas into the reaction chamber so as to be lower than the concentration of the contained gas, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment; And a step.

Another gist of the present invention is a method for removing an organic substance having an ion-implanted region from a substrate using at least a plasma of an oxygen-containing gas. A first step of introducing a fluorine-containing gas into a reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment; and a step of reducing the concentration of the hydrogen-containing gas to hydrogen introduced in the first step. A fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas are introduced into the reaction chamber so as to have a concentration higher than the concentration of the contained gas, a plasma of the gas introduced into the reaction chamber is generated, and a second plasma treatment is performed. And a step.

Another feature of the present invention is a method for removing an organic substance having an ion-implanted region from a substrate using at least a plasma of an oxygen-containing gas. A first step of introducing a fluorine-containing gas into the reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment; and A second step of introducing a gas into which the exposed surface of the base is difficult to be etched into the reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment.

Further, the gist of the method of manufacturing a semiconductor device according to the present invention is a step of forming a patterned organic substance on a substrate having a semiconductor area, and a step of ion-implanting the semiconductor area using the organic substance as a mask. And an organic substance removing step of removing the ion-implanted organic substance from the substrate using at least plasma of an oxygen-containing gas, wherein the organic substance removing step includes an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas. Introduce the contained gas into the reaction chamber,
A first step of generating plasma of the gas introduced into the reaction chamber and performing a plasma treatment, and introducing an oxygen-containing gas into the reaction chamber without introducing a fluorine-containing gas, and introducing the oxygen-containing gas into the reaction chamber A second step of generating gas plasma and performing plasma processing.

The main points of another method of manufacturing a semiconductor device according to the present invention include a step of forming a patterned organic substance on a substrate having a semiconductor area and a step of ion-implanting the semiconductor area using the organic substance as a mask. And an organic substance removing step of removing the ion-implanted organic substance from the substrate using at least plasma of an oxygen-containing gas, wherein the organic substance removing step includes an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas. A first step of introducing a gas containing gas into the reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment;
A second step of introducing a fluorine-containing gas and an oxygen-containing gas into the reaction chamber so as to be 1% by volume or less, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment;
It is characterized by including.

The gist of still another method of manufacturing a semiconductor device according to the present invention is a step of forming a patterned organic substance on a substrate having a semiconductor area, and ion-implanting the semiconductor area using the organic substance as a mask. And an organic substance removing step of removing the ion-implanted organic substance from the substrate using at least plasma of an oxygen-containing gas, wherein the organic substance removing step includes an oxygen-containing gas and a hydrogen-containing gas. Introducing a fluorine-containing gas into the reaction chamber;
A first step of generating plasma of the gas introduced into the reaction chamber and performing a plasma treatment; and a step of reducing the concentration of the fluorine-containing gas to be lower than the concentration of the fluorine-containing gas introduced in the first step. A second step of introducing a contained gas, an oxygen-containing gas, and a hydrogen-containing gas into a reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment.

Another method of manufacturing a semiconductor device according to the present invention includes a step of forming a patterned organic substance on a substrate having a semiconductor area, and a step of ion-implanting the semiconductor area using the organic substance as a mask. And an organic substance removing step of removing the ion-implanted organic substance from the substrate using at least plasma of an oxygen-containing gas, wherein the organic substance removing step includes an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas. A first step of introducing a gas containing gas into the reaction chamber, generating a plasma of the gas introduced into the reaction chamber, and performing a plasma treatment, and a step of reducing the concentration of the hydrogen-containing gas introduced in the first step. A fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas are introduced into the reaction chamber so that the concentration of the gas becomes higher than that of the gas, and plasma of the gas introduced into the reaction chamber is generated. A second step of performing a plasma treatment,
It is characterized by including.

Another method of manufacturing a semiconductor device according to the present invention includes a step of forming a patterned organic substance on a substrate having a semiconductor area and a step of ion-implanting the semiconductor area using the organic substance as a mask. And an organic substance removing step of removing the ion-implanted organic substance from the substrate using at least plasma of an oxygen-containing gas, wherein the organic substance removing step includes an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas. A first step of introducing a contained gas into the reaction chamber, generating a plasma of the gas introduced into the reaction chamber, and performing a plasma treatment; and performing a plasma treatment on the substrate from the gas introduced into the reaction chamber in the first step. Introducing a gas that is difficult to etch the exposed surface of the reaction chamber into the reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma process. That.

Another essential feature of the present invention is an organic substance removing system for removing an organic substance having an ion-implanted region from a substrate, comprising: a container; means for exhausting the inside of the container; A gas introduction device for introducing a gas containing hydrogen, hydrogen, and fluorine, a control device for controlling a flow rate of a gas introduced into the container by the gas introduction device, and a plasma of the gas introduced into the container. A power supply that supplies electrical energy to cause
The control device, after setting the gas introduction device to a first mode for introducing an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas into a reaction chamber, after a predetermined time has elapsed, (1) a mode in which an oxygen-containing gas is introduced into a reaction chamber without introducing a fluorine-containing gas,
(2) a mode in which a fluorine-containing gas and an oxygen-containing gas are introduced into a reaction chamber so that the concentration of the fluorine-containing gas is 0.01% by volume or less, and (3) a concentration of the fluorine-containing gas in the first mode. (4) a mode in which a fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas are introduced into the reaction chamber so as to be lower than the concentration of the fluorine-containing gas introduced in (1); and (4) the concentration of the hydrogen-containing gas in the first mode. A mode in which a fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas are introduced into the reaction chamber so as to be higher than the concentration of the hydrogen-containing gas introduced in step 4.
One of the two modes is set as the second mode.

Further, another gist of the present invention is an organic substance removing system for removing an organic substance having an ion-implanted region from a substrate, comprising: a container; means for exhausting the inside of the container; A gas introduction device for introducing a gas containing hydrogen, hydrogen, and fluorine, a control device for controlling a flow rate of a gas introduced into the container by the gas introduction device, and a plasma of the gas introduced into the container. A power supply that supplies electrical energy to cause
The control device, after setting the gas introduction device to a first mode for introducing an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas into a reaction chamber, after a predetermined time has elapsed, The introduction device may be shifted to a second mode for introducing a gas into the reaction chamber, in which the exposed surface of the substrate is harder to be etched than the gas introduced into the reaction chamber in the first mode.

The fluorine-containing gas is fluorine gas (F ₂ ),
Nitrogen fluoride gas (NF ₃ etc.), sulfur fluoride gas (SF ₆ , S ₂
F ₆ , S ₂ F ₂ , SF ₂ , SF ₄ , SOF _2, etc.), carbon fluoride gas (CF ₄ , C ₂ F ₆ , C ₄ F ₈ , CHF ₃ , CH ₂ F ₂ , CH)
₃ F, C ₃ F _8, etc.), fluorine compound of a rare gas gas (XeF
And the like, which is at least one gas selected from the group consisting of: (1) modifying the region into which ions of the organic substance have been implanted to facilitate removal thereof, and increasing the removal rate of the organic substance.

The hydrogen-containing gas includes hydrogen gas (H ₂ ),
Hydrogen compound gas (H ₂ O, CH ₄ , C ₂ H ₆ , C ₃ H ₈ , CH
_At least one gas selected from the group consisting of ₃ OH, C ₂ H ₅ OH, C ₃ H ₇ OH, etc., and suppresses etching of the surface of the substrate exposed from the organic matter by the fluorine-containing gas.

If the plasma density in the first step is set to 1 × 10 ¹¹ cm ⁻³ or more, the removal rate of organic substances can be increased.

The heating temperature of the base in the first step is set to be equal to or lower than the heating temperature of the base in the second step to suppress the popping of organic substances.

In the first step, fluorine is implanted from the plasma into the organic material into which phosphorus, arsenic, and boron have been implanted, thereby modifying the surface of the organic material.

While monitoring the plasma emission,
The process is shifted from the first process to the second process, or the process is shifted from the first process to the second process after measuring the lapse of time in the first process. As a result, organic substances can be removed with good reproducibility.

Before the region altered by the ion implantation in the first step is removed, the processing is shifted from the first step to the second step, and the etching of the exposed surface of the base is further suppressed. It is preferred for.

The first step and the second step are preferably performed in a common reaction chamber.

The organic substance is, for example, a patterned resist layer.

The base has a surface made of at least one selected from silicon or a silicon compound exposed from the organic substance.

[0038]

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

FIG. 1 is a configuration diagram of a removal system for removing an organic substance such as a photoresist layer according to an embodiment of the present invention.

The photoresist layer removal system shown in FIG. 1 uses a high frequency power such as microwaves to generate 1
The denatured portion of the photoresist layer formed on the semiconductor substrate by ion implantation was modified by high-density plasma of × 10 ¹¹ cm ^-3 or more, specifically about 1 × 10 ¹² cm ^-3 , and further modified. The photoresist layer including the altered portion can be removed by oxygen plasma treatment or the like.

The removal system for removing the photoresist layer shown in FIG. 1 includes a container 1 made of stainless steel or the like for defining a reaction chamber, an exhaust port 2 for exhausting the inside of the container 1, a semiconductor substrate and the like. A heater 4 for heating the substrate 3 attached to the support means for supporting the gas, a gas introduction pipe 5 for introducing gas into the container 1, a dielectric window 6 for transmitting high-frequency power and isolating the inside and outside of the container; , A high-frequency power supply 7 for supplying high-frequency power such as microwaves.

An exhaust device 8 including a vacuum pump and a valve is connected to the exhaust port 2. The exhaust device 8 is operated to exhaust gas in the container 1 through the exhaust port 2.

The gas introduction pipe 5 is connected to a gas introduction device 9 including a valve and a flow controller, an oxygen-containing gas source 10, a fluorine-containing gas source 11, a hydrogen-containing gas source 12, and the like. Then, the gas introduction device 9 is connected to the oxygen-containing gas source 1.
By controlling the flow controllers provided in the respective gas lines of the gas source 11 and the fluorine-containing gas source 11 and the hydrogen-containing gas source 12, the type of gas introduced into the container 1 in each step is determined.

The high frequency power supply 13 is connected to a high frequency power supply 13 such as a microwave power supply.

In this embodiment, a microwave waveguide is used as the high-frequency power supply 7, but other than this, a slot antenna or a rod-shaped antenna can be used.

As the high frequency power supply 13, a VHF power supply or an RF power supply may be used instead of the microwave power supply. In this case, a rod-shaped antenna, a coil, an inductive coupling electrode, a capacitive coupling electrode The plasma can be generated by supplying electric power to the inside of the container by using such a method.

The exhaust device 8, the heater 4, the gas introducing device 9,
The high-frequency power supply 13 can control its operation (on / off timing, gas flow rate, power supply amount, high-frequency power supply amount, and the like) by control signals SG31, SG2, SG1, and SG4 transmitted from the controller 14. It is configured.

In the present embodiment, the position of the heater 4 in the up-down direction is such that the semiconductor substrate 3 mounted on the heater 4 is
The height is set so that ions in the plasma do not reach.

FIG. 2 is a flowchart showing a method of using the removal system for removing the photoresist layer shown in FIG. A method of using the removal system shown in FIG. 1 for removing the photoresist layer will be described with reference to FIG.

First, in the first step, a modification process described below is performed so that a deteriorated portion of the photoresist layer can be removed by oxygen plasma.

A surface of a semiconductor substrate such as a silicon wafer as the substrate 3 is coated with a photoresist layer as an organic substance, and is exposed to a predetermined pattern by an exposure device.
develop. The thus obtained semiconductor substrate with a patterned resist layer made of an organic substance (in this state, it is not necessary to have photosensitivity) is set in an ion implantation apparatus (step S1), and ions such as phosphorus, arsenic, and boron are removed. inject. The ion implanter may be a general line beam implanter or a plasma ion implanter. The sample thus obtained was prepared, and FIG.
The processing shown in FIG.

For example, on a heater 4 heated to about 70 ° C. to 180 ° C., a semiconductor substrate on which a resist layer having a deteriorated portion which is transformed into inashable by ion implantation is formed. I do. Thus, the semiconductor substrate is heated to about 70 ° C. to 180 ° C. by the heater 4.

The appropriate heating temperature is determined depending on the amount of ion implantation (dose amount) and whether or not the resist layer is treated with ultraviolet light (UV). In general, the higher the temperature, the shorter the time required for the modification treatment by the high-density plasma. However, in order to prevent the semiconductor substrate from being contaminated by the popped organic substance, the resist layer is formed so as not to cause the popping. It is necessary to be temperature. Therefore, it is desirable to select 100 ° C. or less here.

Subsequently, the pressure inside the container 1 is reduced by operating the vacuum pump of the exhaust device 8 connected to the exhaust port 2 to, for example, 1.33 × 10 ⁻⁷ Pa (≒ 0.01 × 10 ^7
-7 Torr) or less. Next, the gas introduction system 9 of the gas supply system is switched to the first mode, and a gas containing oxygen, hydrogen and fluorine (for example, a fluorine-containing gas such as SF ₆ , O ₂
And an oxygen-containing gas, a mixed gas) of hydrogen-containing gas such as H _2, is introduced into the exhaust while the vessel 1 through the gas inlet pipe 5 (step S2), such as, the pressure in the vessel 1 From 66.5 Pa to 400 Pa (≒ 0.5 Torr to 3 To
rr).

At this time, the concentration of the oxygen-containing gas is in the range of 50% by volume to 99% by volume, and the concentration of the fluorine-containing gas is 0.1%.
The concentration of the hydrogen-containing gas may be selected from the range of 05% to 5% by volume, and the concentration of the hydrogen-containing gas may be selected from the range of 0.3% to 3% by volume.

Further, in order to adjust the concentration of a predetermined gas or to use it as a carrier gas for the above-described gas, an inert gas such as nitrogen, argon, helium, neon, krypton, or xenon may be used as necessary. It is also preferable to use in addition to the gas.

Examples of the oxygen-containing gas include oxygen gas and oxidized gas.
Nitrogen. Specifically, O _Two, N_TwoO, NO_Two,
CO_TwoAnd so on.

As the fluorine-containing gas, fluorine gas, fluorinated
Examples include fluorine compound gases such as nitrogen, sulfur fluoride, and carbon fluoride.
Can be Specifically, F_Two, NF_Three, SF₆, CF_Four, C_Two
F₆, C_FourF₈, CHF_Three, CH_TwoF_Two, CH_ThreeF, C_ThreeF₈,
S_TwoF_Two, SF_Two, SF_Four, SOF _TwoAnd so on.

As the hydrogen-containing gas, hydrogen gas, water,
Hydrogen compound gases such as hydrocarbons and alcohols are exemplified. Specifically, H ₂ , H ₂ O, CH ₄ , C ₂ H ₆ , C ₃ H ₈ ,
CH ₃ OH, C ₂ H ₅ OH, C ₃ H ₇ OH and the like. When using hydrogen gas, it is preferable to use hydrogen gas diluted to 4% by volume or less with an inert gas.

Then, the microwave as the high frequency power is output at 1500 W, for example, by the high frequency power supply 13 (step S3). The microwave is supplied into the container 1 through a microwave waveguide serving as the high-frequency power supply 7 and a dielectric window.

When high-frequency power is supplied to an atmosphere containing an oxygen-containing gas, a fluorine-containing gas, or a hydrogen-containing gas under the above conditions, a high-density plasma of about 1 × 10 ¹² cm ⁻³ is generated. .

Ozone, oxygen active species, fluorine active species, hydrogen active species, and the like generated by this high-density plasma are imparted to the surface of the resist layer, and the region of the resist layer that has been altered by ion implantation is modified. (Step S4).
This makes it possible to satisfactorily remove the resist layer even by ashing using only the oxygen-containing gas in the second step.

After a predetermined time has elapsed, the supply of the high-frequency power is temporarily stopped, the plasma is turned off, and the process proceeds to the next second step. That is, the controller 14 switches the resist layer removal system from the first mode to the second mode.

The data of the time required for the first step can be calculated in advance from the experimental data. If this is stored in the memory of the controller 14, the first step can be completed by the controller 14 and the second step can be started based on this.

For example, applying and developing a photoresist layer
After patterning by phosphorus (P ⁺) Inject energy
-60 keV, dose 5 × 10^Fifteencm^-2On condition
For the ion-implanted 8-inch semiconductor substrate 3,
1 × 10¹²cm^-3Reforming by high density plasma
Oxygen, fluorine, and hydrogen required for the first step
Is about 30 seconds. Yo
After this time elapses, switch to the second mode
Instead, the procedure may shift to the second step described later.

The mode may be switched based on a signal from the in-situ monitor 15. In other words, CO, H which is a product from the resist layer, or O
And the information SG15 is sent to the controller 14 to switch the mode.

For example, as shown by reference numeral 15 in FIG. 1, using a photodetector for detecting plasma emission intensity, the emission peak wavelength of hydrogen atoms is 656 nm, the emission peak wavelength of oxygen atoms is 777 nm, and the emission peak wavelength of CO is 309 nm. May be measured, and the first step may be terminated and the process may be shifted to the second step according to the result.

In the second step, an ashing process is mainly performed on a portion of the photoresist layer which is not deteriorated by oxygen plasma. In the ashing process, first, while maintaining the temperature of the heater 4 and keeping the container 1 airtight, the container 1 is evacuated by the vacuum pump of the exhaust device 8 connected to the exhaust port 2 until the container 1 becomes almost vacuum. To reduce the pressure. afterwards,
Only pure oxygen gas is introduced from the gas introduction pipe 5 (step S5), and the pressure in the vessel 1 is increased to 39.9 Pa (≒ 0.3T).
orr).

Next, the microwave generated by the high frequency power supply 13 is output at, for example, 1500 W (step S6). This microwave is supplied into the container 1 through the microwave waveguide 7 and the dielectric window 6.

When microwaves are applied to oxygen under the above conditions, high-density oxygen plasma of about 1 × 10 ¹² cm ⁻³ is generated. Ozone, oxygen active species, and the like generated by the oxygen plasma ash the modified resist layer and remove it from the substrate (step S7). When the ashing process is performed under the above conditions, the process can be completed in about 50 seconds.

In the second step, the ashing process is not performed by oxygen plasma using only oxygen. For example, a mixed gas of a fluorine-containing gas and oxygen whose concentration is reduced so as not to corrode the semiconductor substrate. Alternatively, a mixed gas of a hydrogen-containing gas and oxygen that generates hydrogen radicals in plasma may be used. Further, a mixed gas of a fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas may be used.

Specifically, in the case where a fluorine-containing gas is added in the second step, it is desirable to use any one of the following three mixed gases. (1) A fluorine-containing gas and an oxygen-containing gas are introduced into the reaction chamber so that the concentration of the fluorine-containing gas is 0.01% by volume or less. (2) In addition to the fluorine-containing gas and the oxygen-containing gas, a hydrogen-containing gas is introduced into the reaction chamber so that the concentration of the fluorine-containing gas is lower than the concentration of the fluorine-containing gas introduced in the first step. In this case, the concentration of the fluorine-containing gas does not necessarily need to be 0.01 vol% or less. (3) In addition to the fluorine-containing gas and the oxygen-containing gas, the hydrogen-containing gas is introduced into the reaction chamber so that the concentration of the hydrogen-containing gas is higher than the concentration of the hydrogen-containing gas introduced in the first step. In this case, the concentration of the fluorine-containing gas does not necessarily need to be lower than that in the first step.

By doing so, it is possible to reduce the time required for the treatment while preventing corrosion of the base.

As a specific operation of the gas introducing device when shifting from the first step to the second step, after turning off the plasma in the first step, the flow controller of the fluorine-containing gas supply line is controlled. Then, the flow rate may be reduced or the supply may be stopped.

In the second step, if the heating temperature of the base 3 by the heater 4 is increased to, for example, 250 ° C., the time required for the ashing process of the residual resist layer can be shortened, and the plasma generation in the second step The time can be reduced to about 20 seconds.

However, in order to remove the resist layer by this method, it takes time to raise the temperature of the heater 4. Therefore, in the first step, the substrate 3 is not placed on the heater 4 during the generation of the plasma, but is moved above the heater 4 by the moving means provided on the support means.
When the substrate 3 is held away from the substrate 3 and the process proceeds to the second step, the substrate 3 is lowered and the substrate 3 is
It may be placed on top. A known lift pin or the like can be used as a moving unit that can move the base 3 up and down above the heater 4.

Note that the ions in the plasma cause the substrate 3
It is necessary that the position of the substrate 3 moved upward by the moving means to a position where only neutral radicals exist such that ions in the plasma do not reach so as not to be corroded.

Further, depending on the time required for raising the temperature of the heater 4, a measure may be taken to reduce the total time required for removing the resist layer. For example, two removal systems shown in FIG. 1 are adjacent to each other, and one is dedicated to the first step and the other is dedicated to the second step. Using such an apparatus, the substrate 3 that has been subjected to the treatment in the first step at a low temperature is transferred into the other container and placed on the heater 4 already heated to 250 ° C.
The substrate 3 having undergone the above-mentioned steps is placed and subjected to an incineration treatment.

(Method of Manufacturing Semiconductor Device) A method of manufacturing a semiconductor device according to one embodiment of the present invention will be described with reference to FIGS. 3 (a) to 3 (d).

An n-type semiconductor substrate 21 such as a silicon wafer
Is prepared, and an n-type semiconductor layer 23 is epitaxially grown on the surface. A p-type dopant such as boron is diffused to form a p-well 22 made of a p-type semiconductor. An element isolation region 24 made of silicon oxide is formed by selective oxidation. Thermal oxidation of silicon surface to form gate oxide film 2
After forming 5a, 25b, polycrystalline silicon is deposited,
After patterning, the polysilicon gate electrodes 26a, 2a
6b is formed. And apply a photoresist layer,
Exposure, development and patterned resist layer 27
To form Thus, the structure shown in FIG. 3A is obtained.

A source / drain region 28 made of an n-type semiconductor is formed in a region exposed from the resist layer 27 by implanting ions such as phosphorus and arsenic. On the surface side of the resist layer 27, a region 29 altered by ion implantation is formed. Thus, the structure shown in FIG. 3B is obtained.

Note that at the time of ion implantation, n in FIG.
If the mold semiconductor substrate 21 is rotated while being tilted, a deteriorated region is also formed on the side wall of the resist layer 27.

In the same step as the above-mentioned first step, a plasma treatment with a gas containing oxygen, hydrogen and fluorine is performed to modify the resist layer 27. At this time, the ion-implanted altered region 29 may be removed at the same time, or only the reforming may be performed without being removed. Thus, a structure having the n-channel MOS shown in FIG. 3C is obtained.

Subsequently, the process proceeds to the second step, in which plasma treatment with oxygen gas is performed to remove the remaining resist layer 27. The implanted ion species such as phosphorus and arsenic are converted into fluorinated substances and hydrides by the first step and disappear, so that no residue due to the implanted ion species is observed. Thus, the structure shown in FIG. 3D is obtained.

Further, the N-channel MOS portion is covered with a resist layer, and the ion species to be implanted is changed to boron.
3D, a P-channel MO
S can be produced.

According to this embodiment, the resist layer 27 for ion implantation can be formed without excessively etching the polysilicon gate electrodes 26a and 26b and the film on the source / drain regions 28 made of silicon oxide. And can be removed quickly.

(Experiment 1) An 8 inch surface oxidized silicon
Prepare a con wafer and use phenol novolak resin
Applying a photoresist layer for i-line as a component,
Exposure and baking to form a 1 μm thick resist layer film
Formed. Phosphorus (P ⁺) Injecting energy
Lugie 60 keV, dose 5 × 10^Fifteencm^-2Article
Sample 1 was produced by ion implantation according to the conditions.

The above sample was placed on a heated heater in the container, heated to 100 ° C., and the inside of the container was evacuated. Oxygen gas was introduced into the vessel at a flow rate of 2100 SCCM, SF ₆ gas at a flow rate of 3 SCCM, and hydrogen gas diluted to 4% by volume with argon gas at a flow rate of 900 SCCM.

While maintaining the pressure in the container at 133 Pa, a microwave having a frequency of 2.45 GHz and an output of 1500 W was supplied, and plasma of the mixed gas was generated for 40 seconds. The profile of phosphorus and fluorine in the resist layer of the sample that has undergone such processing is analyzed by secondary ion mass spectrometry (SIMS).
Was analyzed by The result is shown in FIG.

A profile of phosphorus and fluorine having a peak concentration near the surface was obtained.

From this, it can be seen that fluorine was implanted into the residual resist layer from fluorine plasma, in addition to phosphorus ion-implanted in advance, and the ion-implanted resist layer was modified. This suggests that as a result of the modification treatment, phosphorus, which is an ion component implanted, is bonded to fluorine in the resist layer.

That is, when phosphorus and fluorine, which are implanted ion components, are bonded by the reforming treatment, the bridge formed between phenol rings, which are components of the resist layer, is cut off. It is considered that the ionic component can be removed as a volatile fluoride during the incineration by performing the oxygen plasma in the step (1).

When the resist layer is modified in this manner, in the subsequent second step, it is possible to reduce the amount of fluorine or to perform ashing of the residual resist layer sufficiently quickly without using fluorine.

[0094]

EXAMPLE 1 A large number of samples 2 (substrates having an ion-implanted resist layer) were manufactured under the same conditions and procedures as in Experiment 1.

One sample 2 was placed on the heated heater 4 in the container 1, heated to 100 ° C., and the inside of the container 1 was exhausted through the exhaust port 2. The gas introducing device 9 and the controller 14 supply oxygen gas at a flow rate of 2100 SCCM, SF ₆ gas at a flow rate of 3 SCCM, and hydrogen gas diluted to 4% by volume with argon gas at 900 SCCM.
At a flow rate of 1.

Then, the pressure in the container 1 is set to 133 Pa (≒
While maintaining the pressure at 1 Torr, a microwave having a frequency of 2.45 GHz and an output of 1500 W was supplied into the container 1 through the high-frequency power supply 7 to generate plasma of the mixed gas for 28 seconds (first step).

Thereafter, the modes were switched by the controller 14 and the gas introducing device 9 to stop the supply of the SF ₆ gas and the hydrogen gas, and the oxygen gas plasma was generated without changing the pressure and the substrate temperature ( Second step).

When the plasma emission intensity due to the components of the resist layer decreased and became substantially constant, the supply of the microwave was stopped and the plasma was turned off.

Then, the sample 2 was taken out of the container 1.

The above processing is performed by setting the plasma generation time in the first step to 0 hours (when there is no first step).
Sample 2 was processed with each change in the range of 80 seconds.
The result is shown in FIG.

FIG. 5 is a diagram showing the relationship between the plasma generation time (reforming time) in the first step and the number of oxide residues on the semiconductor substrate after the ashing process has been performed after the reforming process. It is.

As shown in FIG. 5, for example, when the time for performing the reforming process is up to 28 seconds, the residue of the oxide having a size of 0.2 μm or more on the semiconductor substrate according to the reforming time is determined. Decreases exponentially logarithmically from, for example, about 1 × 10 ⁴ to about 1 × 10 ² .

On the other hand, if the time for performing the reforming treatment exceeds 28 seconds, there is no significant change in the number of oxide residues on the semiconductor substrate. Therefore, it is not preferable that the time for performing the reforming process be much longer than 28 seconds because a portion of the semiconductor substrate on which the resist layer is not formed is corroded.

In the above-described embodiment, when the conditions of the semiconductor substrate to be processed, the resist layer, the heating conditions by the heater, and the like are the same, the time for the reforming process in the first step and the time for the reforming process are performed. Reproducibility was found in the correlation between the oxide residue on the semiconductor substrate and the ashing treatment by oxygen plasma in the second step later.

(Example 2) A silicon wafer having an 8-inch surface oxidized was prepared as a substrate 3, a photoresist layer for i-line was applied, exposed to i-line, developed, and baked. Phosphorus (P ⁺ ) is implanted into the patterned resist layer at an implantation energy of 60 keV and a dose of 5 × 1.
Sample 3 was prepared by ion implantation under the condition of 0 ¹⁵ cm ^-2 .

The sample was placed on the heated heater 4 in the container 1 and heated to 100 ° C., and the inside of the container 1 was evacuated through the exhaust port 2. Oxygen gas was introduced at a flow rate of 2100 SCCM, SF ₆ gas was introduced at a flow rate of 3 SCCM, and hydrogen gas diluted to 4% by volume with argon gas was introduced at a flow rate of 900 SCCM into the vessel 1 by the gas introduction device 9 and the controller 14. .

The pressure in the container 1 was set to 133 Pa (≒ 1 Torr).
r), while maintaining a frequency of 2.45 GHz and an output of 1500
The microwave of W was supplied into the container 1 through the high-frequency power supply 7 to generate plasma of the mixed gas for 40 seconds (first step).

The gas supply device 9 was controlled by the controller 14 to stop the supply of the SF ₆ gas. The temperature and the pressure of the substrate 3 were not changed from the first step, and a microwave was supplied in the same manner as in the first step to generate a plasma of a mixed gas of oxygen and hydrogen for 100 seconds to 120 seconds.

As a result, 0.2 μm
The average of the number of the above residues was 50.

Further, the portion of the base 3 where the resist layer was not formed was corroded only to a thickness of 0.1 nm or less.

[0111]

As described above, the method of removing a resist layer according to the present invention provides a method for removing a deteriorated portion of a resist layer which is ion-implanted by a plasma of a gas obtained by adding a small amount of a fluorine-containing gas to an oxygen-containing gas. Reforming part. At this time, since the hydrogen-containing gas is added, corrosion of the portion exposed from the resist layer due to etching can be suppressed.

Then, the concentration of the fluorine-containing gas is further reduced to 0.01% by volume or less, or the treatment is performed using oxygen gas without using the fluorine-containing gas, or the fluorine-containing gas is reduced and the hydrogen-containing gas is reduced. Plasma treatment is performed by adding or increasing the concentration of the hydrogen-containing gas to remove the modified residual resist layer from the semiconductor substrate almost completely.
Thus, the ion-implanted resist layer can be ashed and removed satisfactorily while suppressing the corrosion of the surface of the semiconductor substrate exposed from the resist layer.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of an organic matter removal system according to an embodiment of the present invention.

FIG. 2 is a flowchart of an organic matter removing method according to an embodiment of the present invention.

FIG. 3 is a schematic view for explaining the method for manufacturing a semiconductor device according to the embodiment of the present invention.

FIG. 4 is a diagram showing a relationship between a distance from a surface of a modified photoresist layer and each concentration of fluorine and phosphorus with respect to the distance.

FIG. 5 is a diagram showing the relationship between the time of a first step and the number of oxide residues on a sample obtained through a subsequent second step.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Container 2 Exhaust port 3 Base 4 Heater 5 Gas introduction pipe 6 Dielectric window 7 High frequency power supply (microwave waveguide) 8 Exhaust device 9 Gas introduction device 10 Oxygen-containing gas source 11 Fluorine-containing gas source 12 Hydrogen-containing gas source 13 High frequency power supply (microwave power supply) 14 Controller

Claims (33)

[Claims] An organic substance removing method for removing an organic substance having an ion-implanted region from a substrate using at least a plasma of an oxygen-containing gas, wherein an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas are reacted. A first step of generating plasma of the gas introduced into the reaction chamber and performing a plasma treatment, and introducing an oxygen-containing gas into the reaction chamber without introducing a fluorine-containing gas. A second step of generating plasma of the gas introduced into the chamber and performing a plasma treatment. 2. A method for removing an organic substance having an ion-implanted region from a substrate using at least a plasma of an oxygen-containing gas, wherein an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas are reacted. A first step of generating a plasma of the gas introduced into the reaction chamber and performing plasma treatment, and a step of generating a plasma of the gas introduced into the reaction chamber, wherein the concentration of the fluorine-containing gas is 0.01% by volume or less. Introducing an oxygen-containing gas into the reaction chamber,
A second step of generating plasma of the gas introduced into the reaction chamber and performing a plasma treatment. 3. An organic substance removing method for removing an organic substance having an ion-implanted region from a substrate using at least a plasma of an oxygen-containing gas, wherein an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas are reacted. A first step of introducing plasma into the chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment, wherein the concentration of the fluorine-containing gas is lower than the concentration of the fluorine-containing gas introduced in the first step. A second step of introducing a fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas into a reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment. A method for removing organic substances. 4. An organic substance removing method for removing an organic substance having an ion-implanted region from a substrate using at least a plasma of an oxygen-containing gas, wherein an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas are reacted. A first step of generating a plasma of the gas introduced into the reaction chamber and introducing the gas into the reaction chamber and performing a plasma treatment; and a step in which the concentration of the hydrogen-containing gas is higher than the concentration of the hydrogen-containing gas introduced in the first step. A second step of introducing a fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas into a reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment. A method for removing organic substances. 5. An organic substance removing method for removing an organic substance having an ion-implanted region from a substrate using at least plasma of an oxygen-containing gas, wherein an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas are reacted. A first step of generating plasma of a gas introduced into the reaction chamber and introducing the gas into the reaction chamber, and performing a plasma treatment; and etching the exposed surface of the substrate with the gas introduced into the reaction chamber in the first step. A second step of introducing a difficult gas into the reaction chamber, generating plasma of the gas introduced into the reaction chamber, and performing a plasma treatment. 6. The gas according to claim 1, wherein the fluorine-containing gas includes at least one gas selected from the group consisting of fluorine gas, nitrogen fluoride gas, sulfur fluoride gas, and carbon fluoride gas.
The organic matter removing method according to any one of the above. 7. The organic matter removing method according to claim 1, wherein the hydrogen-containing gas includes at least one gas selected from the group consisting of hydrogen gas and hydrogen compound gas. 8. The density of plasma in the first step
Is 1 × 10¹¹cm ^-3Any of claims 1 to 5 that are above
2. The method for removing organic matter according to claim 1. 9. The method according to claim 1, wherein a heating temperature of the substrate in the first step is lower than a heating temperature of the substrate in the second step. 10. The method according to claim 1, wherein in the first step, fluorine is further injected from the plasma into the organic substance into which phosphorus, arsenic, and boron have been injected, and the surface of the organic substance is modified. 2. The method for removing organic matter according to claim 1. 11. The organic substance removing method according to claim 1, wherein the processing is shifted from the first step to the second step while monitoring the emission of the plasma. 12. The organic substance removal method according to claim 1, wherein the process is shifted from the first step to the second step after measuring a lapse of time in the first step. Method. 13. The method according to claim 1, wherein the processing is shifted from the first step to the second step before removing the region altered by the ion implantation in the first step. The organic matter removing method according to the above. 14. The method according to claim 1, wherein the first step and the second step are performed in a common reaction chamber.
The organic substance removing method according to the above item. 15. The method according to claim 1, wherein the organic substance is a patterned resist layer. 16. A method of manufacturing a semiconductor device, comprising: forming a patterned organic material on a substrate having a semiconductor region; implanting an ion into the semiconductor region using the organic material as a mask; An organic substance removing step of removing the injected organic substance from the substrate using at least a plasma of an oxygen-containing gas, wherein the organic substance removing step comprises: an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas. Is introduced into a reaction chamber, a plasma of the gas introduced into the reaction chamber is generated, and a first step of performing plasma processing is performed. An oxygen-containing gas is introduced into the reaction chamber without introducing a fluorine-containing gas, A second step of generating plasma of the gas introduced into the reaction chamber and performing a plasma treatment. 17. A method for manufacturing a semiconductor device, comprising: forming a patterned organic material on a substrate having a semiconductor region; implanting an ion into the semiconductor region using the organic material as a mask; An organic substance removing step of removing the injected organic substance from the substrate using at least a plasma of an oxygen-containing gas, wherein the organic substance removing step comprises: an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas. Is introduced into a reaction chamber, a plasma of the gas introduced into the reaction chamber is generated, and a plasma process is performed. The first step includes the steps of: Introducing a gas and an oxygen-containing gas into the reaction chamber,
A second step of generating plasma of the gas introduced into the reaction chamber and performing a plasma treatment. 18. A method for manufacturing a semiconductor device, comprising: forming a patterned organic material on a substrate having a semiconductor region; implanting an ion into the semiconductor region using the organic material as a mask; An organic substance removing step of removing the injected organic substance from the substrate using at least a plasma of an oxygen-containing gas, wherein the organic substance removing step comprises: an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas. Is introduced into the reaction chamber, a plasma of the gas introduced into the reaction chamber is generated, and a plasma process is performed. A fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas are introduced into the reaction chamber so as to be lower, and a plasma of the gas introduced into the reaction chamber is generated. A method of manufacturing a semiconductor device which comprises a second step of performing a plasma treatment, a. 19. A method of manufacturing a semiconductor device, comprising: forming a patterned organic material on a substrate having a semiconductor region; implanting ions into the semiconductor region using the organic material as a mask; An organic substance removing step of removing the injected organic substance from the substrate using at least a plasma of an oxygen-containing gas, wherein the organic substance removing step comprises: an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas. Is introduced into the reaction chamber, a plasma of the gas introduced into the reaction chamber is generated, and a plasma process is performed, and the concentration of the hydrogen-containing gas is the concentration of the hydrogen-containing gas introduced in the first step. A fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas are introduced into a reaction chamber so as to be higher, and plasma of the gas introduced into the reaction chamber is generated. And a second step of performing a plasma treatment. 20. A method of manufacturing a semiconductor device, comprising: forming a patterned organic material on a substrate having a semiconductor region; implanting ions into the semiconductor region using the organic material as a mask; An organic substance removing step of removing the injected organic substance from the substrate using at least a plasma of an oxygen-containing gas, wherein the organic substance removing step comprises: an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas. Is introduced into the reaction chamber, a plasma of the gas introduced into the reaction chamber is generated, and a plasma process is performed; and the exposed surface of the substrate is formed from the gas introduced into the reaction chamber in the first step. Introducing a gas that is difficult to etch into the reaction chamber, generating a plasma of the gas introduced into the reaction chamber, and performing a plasma treatment. The method of manufacturing a semiconductor device according to. 21. The gas according to claim 16, wherein the fluorine-containing gas includes at least one gas selected from the group consisting of fluorine gas, nitrogen fluoride gas, sulfur fluoride gas, and carbon fluoride gas. 13. The method for manufacturing a semiconductor device according to item 10. 22. The method for manufacturing a semiconductor device according to claim 16, wherein the hydrogen-containing gas includes at least one kind of gas selected from the group consisting of hydrogen gas and hydrogen compound gas. 23. The plasma processing apparatus according to claim 16, wherein the density of the plasma in the first step is 1 × 10 ¹¹ cm ⁻³ or more.
13. The method for manufacturing a semiconductor device according to claim 1. 24. The method of manufacturing a semiconductor device according to claim 16, wherein a heating temperature of said base in said first step is lower than a heating temperature of said base in said second step. . 25. In the first step, fluorine is implanted from the plasma into the organic material into which phosphorus, arsenic, and boron have been implanted, and the surface of the organic material is modified.
21. The method of manufacturing a semiconductor device according to any one of items 20 to 20. 26. The method of manufacturing a semiconductor device according to claim 16, wherein the processing is shifted from the first step to the second step while monitoring the emission of the plasma. 27. The semiconductor device according to claim 16, wherein, after measuring a lapse of time in said first step, processing is shifted from said first step to said second step. Manufacturing method. 28. The method according to claim 16, wherein the processing is shifted from the first step to the second step before removing a region altered by ion implantation in the first step. The manufacturing method of the semiconductor device described in the above. 29. The method according to claim 16, wherein the first step and the second step are performed in a common reaction chamber.
13. The method for manufacturing a semiconductor device according to the above item. 30. The method according to claim 16, wherein the organic substance is a resist layer formed of a photosensitive resin.
13. The method for manufacturing a semiconductor device according to the above item. 31. The method of manufacturing a semiconductor device according to claim 16, wherein the base includes a surface made of at least one selected from silicon or a silicon compound exposed from the organic substance. 32. An organic substance removing system for removing an organic substance having an ion-implanted region from a substrate, comprising: a container; means for exhausting the inside of the container; and a gas containing oxygen, hydrogen, and fluorine in the container. A gas introduction device for introducing gas, a control device for controlling a flow rate of gas introduced into the container by the gas introduction device, and an electric energy for causing plasma of the gas introduced into the container. And a control unit that sets the gas introduction device to a first mode in which an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas are introduced into a reaction chamber, and a predetermined time has elapsed. Then, the gas introducing device is operated in the following manner: (1) a mode in which an oxygen-containing gas is introduced into a reaction chamber without introducing a fluorine-containing gas; and (2) a concentration of a fluorine-containing gas of 0.01 body. % In which the fluorine-containing gas and the oxygen-containing gas are introduced into the reaction chamber so that the concentration of the fluorine-containing gas is not more than the concentration of the fluorine-containing gas introduced in the first mode. A mode in which a fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas are introduced into a reaction chamber; and (4) the concentration of the hydrogen-containing gas is higher than the concentration of the hydrogen-containing gas introduced in the first mode. A mode in which a fluorine-containing gas, an oxygen-containing gas, and a hydrogen-containing gas are introduced into a reaction chamber;
An organic matter removal system, which is set as a mode. 33. An organic substance removing system for removing an organic substance having an ion-implanted region from a substrate, comprising: a container; means for exhausting the inside of the container; and a gas containing oxygen, hydrogen and fluorine in the container. A gas introduction device for introducing gas, a control device for controlling a flow rate of gas introduced into the container by the gas introduction device, and an electric energy for causing plasma of the gas introduced into the container. And a control unit that sets the gas introduction device to a first mode in which an oxygen-containing gas, a hydrogen-containing gas, and a fluorine-containing gas are introduced into a reaction chamber, and a predetermined time has elapsed. Then, the gas introducing device is introduced into the reaction chamber in a gas in which the exposed surface of the substrate is harder to be etched than the gas introduced into the reaction chamber in the first mode. , Organic matter removing system characterized by shifting.