JP3402837B2 - Processing method of magnetic thin film - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to Fe, Co or Ni.
TECHNICAL FIELD The present invention relates to a method for processing a magnetic thin film made of a magnetic material that contains

[0002]

2. Description of the Related Art Magnetic thin films made of magnetic materials containing Fe, Co or Ni have been widely used in magnetic devices such as magnetic heads, magnetic disks, magnetic bubble memories, magneto-optical disks, magnetic sensors and thin film inductors. The magnetic random access memory (M
It is expected to develop into RAM) and spin polarization effect (SP) elements. Among these magnetic material devices, it is indispensable to perform desired patterning on the magnetic material thin film in order to produce a thin film magnetic head, a magnetic sensor, a magnetic bubble memory, a thin film inductor, an MRAM, and an SP element. Also for disks and magneto-optical disks, it is preferable to perform desired patterning on the magnetic thin film in order to form recording tracks and impart shape anisotropy.

Conventionally, the ion milling method has been mainly used to perform desired patterning on the magnetic thin film. This is a method of ionizing and accelerating an inert gas such as Ar to collide with the magnetic thin film. If the ion density is high, a high etching rate can be obtained, and it is sufficient if the angle of collision of ions can be appropriately set. Anisotropy can be imparted. However, in the ion milling method, if the thickness of the magnetic thin film is large, there is no material selectivity, so it becomes impossible to process, and even when processing a large area magnetic thin film at the same time, a large ion source is required and it is not economical. However, there is a limit to the enlargement of the ion source from the technical point of view.
Furthermore, in the ion milling method, it is difficult to perform fine patterning with high precision because part of the workpiece that is released into the gas phase during processing reattaches to the sidewalls of the mask and reduces processing accuracy. It was

When manufacturing a thin film magnetic head, etc.,
A magnetic thin film having a predetermined pattern is also directly obtained by a plating method. For example, NiFe plating in a resist frame pattern is a typical one.
However, it is difficult to stably supply the plating liquid to the pattern forming part, the composition of the plating liquid tends to vary inside and outside the pattern forming part, and it is easy to change with time. It is expected that the formation of the magnetic thin film pattern of 1 cannot be sufficiently dealt with.

[0005]

As described above, the ion milling method, which has been mainly used so far in processing a magnetic thin film, has a problem in terms of material selectivity and economical efficiency, and is fine. It was also extremely difficult to perform patterning with high accuracy. On the other hand, as a thin film processing method other than the ion milling method, reactive ion etching (RIE) is used.
The plasma etching method using a reactive gas represented by the above has been known for a long time, and particularly in the LSI manufacturing process, it is preferable in terms of material selectivity and economical efficiency, and activated reactive gas is a normal LSI material. Since a reaction product having a high vapor pressure between and is easily generated, it is widely used for fine patterning. However, when the same plasma etching method is applied to the processing of the magnetic thin film, the vapor pressure of the reaction product of the reactive gas and the magnetic material generally used in the LSI manufacturing process is low and fine patterning is performed. In this case, it is necessary to heat the magnetic thin film to a high temperature, which is not practical.

For example, IEEE Trans. Magn. 27 (6), 4888,1
991 and Japanese Unexamined Patent Publication (Kokai) No. 3-97877 reported that a magnetic thin film made of Fe-Si-Al was processed by RIE using an activated chlorine-based gas. Specifically, CCl ₄ , Cl ₂ , CCl
₃ F are shown. However, for example, 100 nm
The substrate temperature must be set to about 300 ° C. or more in order to perform processing at a high etching rate of about / min or more, which cannot be used in the manufacturing process of the magnetic device as described above.

In Japanese Patent Laid-Open No. 4-129014, F
A rare gas, Cl ₂ , CCl ₄ , and CHCl are formed on the exposed portion of the magnetic thin film made of a magnetic material containing e, Co, or Ni.
A technique for processing a magnetic thin film by supplying a mixed gas of ₂ F or CCl ₂ F ₂ has been disclosed, but the etching rate is as low as 20 nm / min, which is not practical. Moreover, although chloride, which is a reaction product of the magnetic material and the chlorine-based gas, is generated in the exposed portion of the magnetic thin film, essentially, the magnetic thin film in the exposed portion is processed only by physical etching of a rare gas. Since it is carried out, there is a problem that the material selectivity is poor and the processing accuracy is lowered due to the reattachment of the workpiece.

In view of the above problems, the present invention is excellent in material selectivity and economical efficiency, and it is possible to perform fine patterning at a low temperature at a high speed and with high accuracy even on a magnetic thin film over a large area. It is an object of the present invention to provide a method for processing a magnetic thin film.

[0009]

The present invention made to achieve the above object has a predetermined pattern on a magnetic thin film made of a magnetic material containing at least one of Fe, Co and Ni. A mask is disposed, a reactive gas containing activated BCl ₃ is supplied to the exposed portion of the magnetic thin film to react with the magnetic material, and then the exposed magnetic thin film is removed. This is a method of processing a magnetic thin film in which desired patterning is performed on the magnetic thin film. That is, in the present invention, for example, reactive ion etching (R
In a method of processing a magnetic thin film utilizing a chemical reaction such as IE) or chemical dry etching (CDE), it is characteristic that activated BCl _{3 in a} plasma state is used as a reactive gas. Therefore, first, the mechanism of removing the exposed portion of the magnetic thin film by supplying the activated BCl ₃ will be compared with the case where the activated Cl ₂ is used.

In the present invention, when BCl ₃ is activated in a reaction chamber or the like where a magnetic thin film is processed, chlorine ions or radicals and B-Cl type ions or radicals are generated. Of these, chlorine ions or radicals react with the magnetic material when supplied to the exposed portion of the magnetic thin film, and are similar to active species of Cl ₂ , Fe, Co,
Ni chloride is formed.

On the other hand, in the present invention, the B-Cl-based ion or radical generated together with the chlorine ion or radical is involved in the progress of the physical etching of the exposed portion of the magnetic thin film, and the chlorine ion or radical as described above. Fe, Co, N, which are reaction products of
Promote desorption and volatilization of chloride i. Therefore, the activation energy at the time of evaporating and desorbing and volatilizing the reaction product is remarkably reduced, and it becomes possible to perform processing at a very high speed even at a low temperature.

On the other hand, when chlorine ions or radicals generated by the activation of Cl ₂ are supplied to the exposed portion of the magnetic thin film, chloride is generated in the exposed portion of the magnetic thin film, which is similar. The activation energy when evaporating, desorbing and volatilizing the reaction product is determined only by the chemical vaporization energy of the produced chloride, without the elimination being physically promoted. That is, if chlorine ions or radicals are supplied alone, the reaction products are desorbed and volatilized based only on the vapor pressure of chloride, which is a reaction product, and physical etching can hardly be expected.

Therefore, when activated Cl ₂ is used as a reactive gas, the vapor pressures of the reaction products of chlorides of Fe, Co and Ni, especially Co and Ni chlorides and divalent Fe chlorides, are increased. However, in order to perform processing with a high etching rate, heating at a high temperature of about 400 ° C. or higher is required. Moreover, in processing at a high temperature of about 400 ° C. or higher, no matter how activated reactive gas is used, the mechanism for removing the exposed portion of the magnetic thin film is dominated by mere thermal reaction and thermal evaporation. This makes it difficult to carry out anisotropic processing that should be realized.

When a carbon chloride-based active species such as CCl ₄ is supplied to the exposed portion of the magnetic thin film, the C--Cl-based ion or radical generated together with the chlorine ion or radical is B in the present invention. Like the -Cl-based ions or radicals, it participates in the progress of physical etching of the exposed portion of the magnetic thin film. However, during processing of the magnetic thin film, carbon, which has a depositability by itself, is easily deposited on the surface to be processed, the etching rate is still poor, and it is difficult to secure sufficient processing accuracy. Further, carbon chloride gas and its active species pose a serious problem of pollution.

In the method of processing a magnetic thin film of the present invention, the density of chlorine ions or radicals in the reactive gas is reduced by using the activated BCl ₃ and the activated Cl ₂ together. Therefore, the magnetic thin film can be processed at a lower temperature and a higher speed. That is, BCl ₃ alone produces a large amount of lower chlorides such as subchlorides which do not sufficiently react with chlorine ions or radicals, and such a low chloride residue having a low vapor pressure tends to be generated after processing. On the other hand, when activated Cl ₂ is used in combination, at least a part of the lower chloride is converted into chloride having a stoichiometric composition, the vapor pressure of the reaction product is increased, and the activation energy of evaporation is increased. In addition to contributing to the reduction, the generation of residues is significantly suppressed, and as a result, the processing accuracy is improved. Therefore, it becomes possible to perform a high etching rate and a high precision processing at a lower temperature.

[0016] For the mixing ratio of BCl ₃ and Cl _2, where the total amount of Cl ₂ amount of BCl ₃ and Cl ₂ is 0
The flow rate ratio when introducing into the reaction chamber may be adjusted so as to be about 90 vol%, preferably 40 to 85 vol%, and more preferably about 70 vol%. What if
If the amount of Cl ₂ is too small, the generation of lower chloride residues is not effectively suppressed, while if the amount of Cl ₂ is too large, BC
This is because the promotion of desorption and volatilization of chlorides of Fe, Co, and Ni by the l-type ions or radicals may be insufficient. Although there are gases other than Cl ₂ that generate chlorine ions or radicals upon activation, at least carbon chlorides such as CCl ₄ should be excluded from the pollution problem. In this respect, Cl ₂ as described above
Is also preferable from the viewpoint of simplicity of exhaust gas treatment after being activated.

Further in the present invention, activated BCl ₃
By using a deposition gas together with activated Cl ₂ and a deposited gas, a deposition film of a deposit is formed on the side wall of the magnetic thin film that is removed by etching during the processing of the magnetic thin film, and the anisotropic shape of the processed shape is obtained. Is improved. That is, in the magnetic thin film processing method of the present invention, it is possible to perform sufficient anisotropic processing by adjusting the density and energy of the active species as described above, even if the deposition gas is not used together. However, if the deposition gas is also used to form the adhered film on the side wall of the pattern of the magnetic thin film, the anisotropy of the processed shape can be made more remarkable.

Moreover, when the deposition gas is used together, it is difficult for the deposited film to be formed on the processed surface of the magnetic thin film, which is susceptible to ion bombardment, and it is selectively formed only on the side wall of the pattern of the magnetic thin film. Therefore, it is very preferable for anisotropic processing. Further, the deposited film thus formed contributes to the protection of the magnetic thin film, which is generally low in corrosion resistance, and the adhesion of the non-magnetic film between the patterns of the magnetic thin film. Corrosion is suppressed, and the reliability of the magnetic device using the pattern of the obtained magnetic thin film is improved.

In the present invention, as such a deposition gas, the dissociated species excited in plasma or the like form BCl ₃ or a compound with a constituent element of the magnetic thin film, and form a side wall of the pattern of the magnetic thin film. As long as it can be adhered to SiCl ₄ , O ₂ , N ₂ , CO, TiCl
₄ , CH ₂ F ₂ , CH _{3 and the} like are exemplified. Among these, from the viewpoints of ease of handling, etching etching selectivity to mask, securing etching rate in the thickness direction of the magnetic thin film, and low-temperature processability, SiCl ₄ , O ₂ , N ₂ ,
CO is preferred. In addition, in particular, when these are excited in plasma, the amount of chlorine ions or radicals in the reactive gas can be increased, so that SiCl ₄ and T
iCl ₄ is preferred.

Of these, SiCl ₄ is a deposition gas which is preferably used together with activated BCl ₃ . That is, generally, amorphous Si produced when dissociated species of SiCl ₄ is deposited is easily etched by chlorine ions or radicals generated by activation of chlorine-based gas, and even if formed as an adhered film, Poor stability. However, SiCl ₄ is activated to BCl ₃
When used together with, the p-type amorphous Si doped with B is deposited as a deposition film, and this p-Si is difficult to exchange electrons with chlorine radicals. This is because a sufficiently stable adherend film can be obtained.

[0021] If a specific deposition gas as described above is used in the present invention, respectively as an adherend film of the side wall of the pattern of the magnetic thin film, the SiCl ₄ amorphous Si, O ₂
Is an oxide of a constituent element of the magnetic thin film, and N ₂ is BCl ₃
Boron nitride, which is a reaction product of N with N ₂ , oxides of carbon and constituent elements of the magnetic thin film in CO, Ti in TiCl _4.
Can be attached. Note that O ₂ is particularly effective when processing a magnetic thin film containing an oxidative active element as a constituent element, and for example, CoZrNb containing Zr as a constituent element.
With respect to the film, an oxide of Zr and an oxide of Si or Al for the FeSiAl film having Si and Al as constituent elements can be easily deposited on the side wall of the magnetic thin film as an adhered film.

Further, in the present invention, a deposition gas may be appropriately combined and used, and particularly SiC is used as the deposition gas.
When L ₄ or TiCl ₄ and O ₂ are used together, Si or Ti
When N ₂ is used in combination with the above oxide, SiCl ₄ or TiCl ₄ , the nitride of Si or Ti can be deposited. At this time, instead of O ₂ and N ₂ , N ₂ O and NH ₃ are replaced by SiCl.
Similarly, oxides or nitrides of Si or Ti can be adhered even when used in combination with ₄ or TiCl ₄ , but it is preferable to use O ₂ or N ₂ from the viewpoint of simplicity of exhaust gas treatment.

In the present invention, particularly when CO is used as the deposition gas, activated BCl ₃ or Cl
CO also functions as a reducing agent for chlorides of Fe, Co, and Ni, which are reaction products of ₂ and the magnetic material. Therefore,
Since a part of the chlorides of Fe, Co, and Ni are converted into a carbonyl compound having an extremely high vapor pressure, the magnetic thin film can be processed at a much lower temperature and a higher speed as a result. Further, at this time, an active metal serving as a catalyst component when the chlorides of Fe, Co and Ni are carbonylated, specifically, Li and N
CO for a, K, Rb, Cs, Mg, Al, Zn, Cu, etc.
When it is supplied to the exposed part of the magnetic thin film together with this, the conversion rate of the chloride to the carbonyl compound increases, which is effective.

Here, in supplying the catalyst component to the exposed portion of the magnetic thin film, Li, Na, K, Rb, Cs, and M are supplied.
Although simple substances of g, Al, Zn, and Cu may be used, compounds containing them such as hydrides such as lithium hydride, amalgams such as sodium amalgam, and organic metals such as organic lithium and organic aluminum are used. You can also In addition, these may be in any form of solid, liquid and gas, and depending on the form, they are appropriately arranged in the gas introduction system of the reaction chamber where the sample on which the magnetic thin film is formed or in the vicinity of the sample. As a result, the element serving as the catalyst component can be supplied to the exposed portion of the magnetic thin film.

The mixing ratio of the deposition gas in the present invention is
It is preferable that the flow rate ratio when introducing into the reaction chamber is adjusted so that the total amount of BCl ₃ and Cl ₂ is about 5 to 30 vol%, and further about 15 vol%. If the mixing ratio of the deposition gas is small, the deposited film is not sufficiently formed on the side wall of the pattern of the magnetic thin film, and conversely, if the mixing ratio of the deposition gas is large, deposits are formed on the work surface. This is because there is a risk that the film will be deposited and the etching rate will decrease. When SiCl ₄ and O ₂ or N ₂ are used together as the deposition gas, the amount of SiCl ₄ in the total deposition gas is 25
It is preferably set to about 75 vol%.

In the present invention, the above-mentioned gases include rare gases such as He, Ne, Ar, Kr and Xe and H.
_It may be diluted with a carrier gas such as ₂ and introduced into the reaction chamber. For activation of these gases, electrical methods such as plasma discharge, optical methods such as ultraviolet light irradiation, thermal methods such as heating, etc. can be used. Further, these can be used together, but it is preferable to supply the reactive gas in the plasma state to the exposed portion of the magnetic thin film by utilizing at least an electric method such as plasma discharge.

Here, when the reactive gas containing BCl ₃ or the like activated by the electric method is supplied to the exposed portion of the magnetic thin film to process the magnetic thin film,
The processing temperature is preferably set to 100 ° C or higher and 300 ° C or lower. That is, in the present invention, if the exposed portion of the magnetic thin film is etched at a processing temperature of 100 ° C. or higher using a reactive gas that has been activated by discharge, a magnetic thin film with a practically sufficient high etching rate can be obtained. Processing is possible. However, if high speed processing is not required, 100 ℃
The magnetic thin film may be processed at a processing temperature of less than 100 ° C., but at a processing temperature of less than 100 ° C., a large amount of residues such as the above-mentioned lower chlorides tend to be generated.

On the other hand, if the processing temperature exceeds 300 ° C., the mere thermal reaction and thermal evaporation in the exposed portion of the magnetic thin film become dominant, and the anisotropy of the processed shape may decrease.
In other words, the lower limit value of the temperature at which the etching of the exposed portion of the magnetic thin film proceeds based on mere thermal reaction and thermal evaporation without being discharged is 300 ° C. When the processing temperature is 300 ° C. or lower, mere thermal reaction and thermal evaporation do not substantially pose a problem, and anisotropic processing by the discharge-activated reactive gas sufficiently proceeds. Further, for a general magnetic substance device using a magnetic substance thin film, a temperature of 300 ° C. or lower corresponds to the heat resistant temperature of most substrates or films normally included in the magnetic substance device, and therefore, the magnetic substance thin film of the present invention can be used. When the processing temperature is set to 300 ° C. or less in the processing method, the range of application is significantly expanded.

At this time, in order to perform sufficient anisotropic processing, the discharge density on the magnetic thin film should be 1 to 10 W / cm.
^{2. The} cathode drop voltage formed near the surface of the magnetic thin film is set to 0.
It is preferable to set it to 5 to 2.5 kV to adjust the density and energy of the generated plasma. That is, the discharge density is less than 1 W / cm ² , or the cathode drop voltage is 0.5 k.
If it is less than V, especially when the magnetic thin film is processed at a temperature near 300 ° C., the thermal reaction and thermal evaporation dominate in the exposed portion of the magnetic thin film, and the anisotropy of the processed shape decreases. Sometimes. On the other hand, if the discharge density exceeds 10 W / cm ² or the cathode drop voltage exceeds 2.5 kV, the magnetic thin film may be damaged due to severe discharge conditions, and physical etching may proceed rapidly enough. There is a possibility that a high etching selectivity ratio to mask may not be obtained. Further, the discharge density is desired to be set higher as the processing temperature of the sample is lower. For example, when the processing temperature is as low as about 100 ° C., the preferable discharge density is 2 W / cm ² or more.

The discharge density and the cathode drop voltage depend on the gas and the gas pressure introduced into the reaction chamber, and in the method of processing a magnetic thin film of the present invention, the gas pressure, the discharge density and the cathode drop voltage. If two of them are decided, the other one will be decided at the same time. Here, in the present invention, the gas pressure in the reaction chamber when the discharge density and the cathode drop voltage are set as described above is approximately 5 to 50 Pa.

Further, in the present invention, a mask having a predetermined pattern is usually arranged on the magnetic thin film formed on the substrate. The mask at this time is resist, carbon, silicon oxide, aluminum oxide, Silicon nitride,
Aluminum nitride or the like can be used, and of these, the resist is particularly preferable because of the simplicity of the manufacturing process.
However, when processing the magnetic thin film at a temperature of about 150 ° C. or higher, which is higher than the resisting temperature of the resist, first, silicon oxide, aluminum oxide or the like is formed on the magnetic thin film, and a predetermined pattern is formed on the film. A resist is formed and exposed portions of silicon oxide and aluminum oxide are etched at a low temperature. After transferring a pattern, the resist is peeled off by ashing or the like. Then, the magnetic thin film may be processed using the film of silicon oxide, aluminum oxide, etc., to which the predetermined pattern is transferred as described above, as a mask. Furthermore, the substrate is not particularly limited, and usually includes a ferrite substrate, a glass substrate, a silicon substrate, and the like.
In the present invention, since a magnetic thin film can be processed especially at low temperature, a resin substrate may be used.

In the present invention, specifically, Fe, Co and Ni simple substances and their alloys, as well as FeN, FeSiAl and Co are used.
It can be widely applied to magnetic thin films made of magnetic materials such as FeN, CoZrNb, and CoFeSiB. That is, the method for processing a magnetic thin film of the present invention uses a reactive gas that can physically promote the desorption of the reaction product after the reaction product is generated between the magnetic material and the magnetic material. Therefore, the magnetic thin film can be selectively and collectively processed with high etching rate and high accuracy even at a low temperature. In the present invention, in order to reduce the processing time, for example, a rare gas such as Ar, which is appropriately used in combination with the activated reactive gas, is electrically supplied with energy to be accelerated and supplied to the exposed portion of the magnetic thin film. It is also possible to do so.

[0033]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic configuration diagram of an RIE experimental apparatus used for carrying out the present invention. In FIG. 1, 1 is a reaction chamber, 21 is a discharge cathode, 22 is a sample stage, 3 is a sample, 4 is a capacitively coupled high-frequency power source, 5 is a counter electrode, 61 is a gas supply source, 62 is a gas flow rate regulator, and 63. Is a gas supply ring, 7
1 is an infrared lamp for heating a sample, 72 is a lamp housing surface for condensing, 73 is a quartz window for transmitting infrared rays, 8 is a gas exhaust system, 9 is a cathode drop voltage monitor, 10 is a sample temperature monitor,
Reference numeral 11 is a gas pressure gauge.

Here, SUS was used for the reaction chamber 1, and an Al plate subjected to alumite treatment for the purpose of preventing corrosion due to chlorine-based gas was arranged on the inner wall portion. Further, SUS was used for the cathode 21 as well, and the cathode 21 was coated with an aluminum cylinder which was also anodized. The sample table 22 is made of a quartz plate having a diameter of 18 cm.

On the other hand, the capacitive coupling type high frequency power source 4 having a frequency of 13.56 MHz and a maximum power of 4 kW is used.
The discharge cathode 21 was capacitively coupled to form a cathode drop voltage in the vicinity of the sample table 22. The counter electrode 5 was made of an alumite-treated Al ring, and the central portion was made mesh-shaped to irradiate the sample 3 with infrared rays. The counter electrode 5 is for uniformizing the discharge density on the sample 3,
It does not need to be installed in particular.

As the gas supply source 61, BCl ₃ , Cl ₂ , SiCl ₄ and CO gas cylinders inside the cylinder cabinet and O ₂ and N ₂ gas cylinders housed in a cylinder stove outside the cylinder cabinet are set as pressure regulators. It is connected to the gas flow rate adjuster 62 by an SUS pipe via. With respect to the gas cylinders in the cylinder cabinet, a nitrogen line for purging was connected to each gas system, and all gas lines were in a nitrogen purge state when not operating. Here, each gas line is naturally independent until it passes through the gas flow rate regulator 62, and at the outlet side of the gas flow rate regulator 62, these gas lines are connected and introduced into the reaction chamber 1. There is. Moreover, each of these gas lines is connected to the reaction chamber 1.
The bypass line is provided which connects directly to the gas exhaust system 8 without passing through, and not the gas line of N ₂ in the reaction vessel for purging was in addition to the separately provided (illustrated gas line of N ₂ in the gas supply source 61 ).

Further, the gas supply ring 63 is formed by forming a large number of holes having a diameter of 2 mm in a SUS pipe and then winding it in an annular shape to make the gas flow in the reaction chamber 1 uniform.
It does not matter if gas is directly introduced from the inner wall of the reaction chamber 1 without providing this. On the other hand, the sample heating infrared lamp 71, the concentrating lamp housing surface 72, and the infrared transmitting quartz window 73 are used for the sample 3 having a small area for experiments.
It is provided for the purpose of heating to a high temperature of about 0 ° C,
In the method for processing a magnetic thin film of the present invention, which requires heating at about 300 ° C. or lower, it is more preferable to use an infrared lamp source having a low light condensing degree or to embed a sheathed heater in the discharge cathode 21 or the sample table 22. It is practically preferable for processing a magnetic thin film over an area. When the sheathed heater is embedded in the discharge cathode 21 for heating, it is possible to introduce gas from above the reaction chamber 1 in which the infrared transmitting quartz window 73 is provided. By providing a porous disk or the like, it is possible to realize uniform gas flow and uniform discharge density at the same time.

A dry pump was used for the gas exhaust system 8 as in the case of an ordinary RIE apparatus. The ultimate vacuum is about 0.5 Pa. The cathode drop voltage monitor 9 is a system in which a high frequency and high breakdown voltage probe is installed on the power supply line of the discharge cathode 21 and observation is performed with an oscilloscope. As the sample temperature monitor 10, a hole having a diameter of 1 mm was opened in the sample table 22 immediately below the sample 3, and a thermocouple was inserted therein. Furthermore, the lead of this thermocouple is taken out of the reaction chamber 1 through the vacuum introduction terminal,
Connect to the temperature controller via CR filter,
The temperature of the sample 3 during discharge was controlled to be substantially constant by turning on the infrared lamp 71 for heating the sample according to the output of the temperature controller. 1 for gas pressure gauge 11
A 33 Pa head diaphragm type and a Pirani gauge were used in combination, and the gas pressure in the reaction chamber 1 was monitored by the diaphragm type when processing the magnetic thin film and the Pirani when exhausting.

Next, FIG. 2 is a sectional view showing the structure of the sample 3 used in the experiment here. In FIG. 2, reference numeral 31 is a Si substrate, and the reason for using the Si substrate 31 is that the handling and the formation of the mask 34 thereon are easy. However, since Si is corroded by the chlorine-based gas, the SiO ₂ sputtered film 3 with a film thickness of 200 nm acts as an etching stopper between the Si substrate 31 and the magnetic thin film 33.
2 is formed. The magnetic thin film 33 mainly has a film thickness of 1 μm.
Co ₈₇ Zr ₅ Nb ₈ film was used, but NiF
The e film, the FeSiAl film, and the Co film were subjected to the experiment. The magnetic thin film 33 was formed by the sputtering method in any case.

Further, a mask 34 having a predetermined pattern is arranged on the magnetic thin film 33. Specifically, first, a 200 nm thick SiO film is formed on the magnetic thin film 33.
_Two films were formed by sputtering, and then a resist pattern composed of lines and spaces of several kinds of widths was formed on the SiO ₂ film by using a normal photolithography technique. Then, this is housed in a RIE device for SiO ₂ and C
The resist pattern was transferred to the SiO ₂ film by etching using HF ₃ gas to form a mask 34 having a pattern of predetermined line and space, and then the resist pattern was removed using a resist asher.

The sample 3 as shown in FIG. 2 is prepared when the cross-sectional SEM image is observed after the magnetic thin film is processed to evaluate the processed shape, and when the processed shape is not evaluated,
Using a sample 3 in which a 3 mm square quartz plate having a thickness of 0.5 mm is directly placed as a mask 34 on the magnetic thin film 33, R
The etching rate at the time of IE was measured. At this time, in all cases, the etching rates were completely the same.

In this example, the sample 3 as described above was processed into a magnetic thin film as follows using the apparatus shown in FIG. First, the sample 3 is placed on the sample table 22 of the apparatus shown in FIG.
Was installed and the inside of the reaction chamber 1 was evacuated. Next, the temperature controller of the sample temperature monitor 10 is set to a desired temperature, the sample heating infrared lamp 71 is turned on, the temperature of the sample 3 is raised to a set value, and after reaching a constant temperature, the gas supply source 61 and the gas are supplied. Gas was introduced into the reaction chamber 1 by operating the flow rate controller 62.

After the gas pressure in the reaction chamber 1 reaches a constant value,
Immediately after that, the capacitively coupled high-frequency power source 4 is operated to operate the discharge cathode 2
A glow plasma of a reactive gas was generated above 2 and processing of the magnetic thin film by RIE was continued for a predetermined time. Subsequently, the operation of the capacitively coupled high-frequency power source 4 and the introduction of gas into the reaction chamber 1 are immediately stopped, the infrared lamp 71 for heating the sample is turned off, and the vacuum is applied until the temperature of the sample 3 drops to 50 ° C. or lower. The sample 3 was taken out of the reaction chamber 1 after being left in the atmosphere or N ₂ stream. Further, in the sample 3 on which the magnetic thin film was processed in this manner, the processed shape was evaluated by observing the cross-sectional SEM image, and the etching rate was calculated by the stylus type film thickness meter. In addition, micro-Auger electron spectroscopic analysis (μAES) was used as needed.

Next, the experimental examples specifically carried out here will be described in detail. The following experimental examples were all carried out in a parallel plate type RIE experimental device utilizing capacitive coupling discharge, but the magnetic thin film processing method of the present invention is not limited to this.
For example, various modifications such as RIE using magnetron discharge, RIE using inductively coupled discharge, RIE using electron cyclotron resonance discharge, etc. can be made without departing from the scope of the present invention. [Experimental Example 1] BCl ₃ , Cl for samples having a Co ₈₇ Zr ₅ Nb ₈ film or a Co film formed as a magnetic thin film.
₂ or mixed gas of these, discharge density 1.2W
/ Cm ² , the cathode drop voltage was set to about 0.65 kV, the processing temperature T of the sample was changed, and the magnetic thin film was processed by RIE. However, the gas pressure in the reaction chamber at this time is 7 to 15 Pa, and the total gas flow rate is 100 to 200 sccm.
Is. In addition, here, the capacitive coupling type high frequency power source of the device is not operated appropriately, the sample is left in a gas stream which is not discharge activated for a predetermined time, and the progress of etching of the exposed portion of the magnetic thin film is observed, In the experiment, contribution of etching due to thermal reaction and thermal evaporation was investigated.

First, FIG. 3 is an experimental result showing the relationship between the processing temperature T and the etching rate when pure Co ₂ was introduced at a flow rate of 100 sccm to process the CoZrNb film and the Co film. In the figure, the black circles are the CoZrNb film and the black triangles are the Co film, and the results were obtained by processing with discharge-activated Cl ₂ as a reactive gas. As a result, ○ and △ are the same without operating the capacitive coupling type high frequency power supply. The results of trial processing of CoZrNb film and Co film by introducing pure Cl ₂ into the reaction chamber are shown in FIG.

In this case, the activation energy Ea of etching calculated from the inclination of the figure is about 0.9 eV, which is not a value greatly different from the evaporation energy 1.24 eV of CoCl ₂ which is the reaction product here. . Therefore, it can be seen that the promotion of desorption of reaction products due to physical etching can hardly be expected, and if a gas that is not discharge activated is actually used, the etching does not proceed and the etching due to thermal reaction and thermal evaporation is ignored. At a processing temperature of 300 ° C or less, the etching rate is 15 to 20 nm.
It can be confirmed from FIG. 3 that it is as low as / min. In addition, when the activation energy Ea of etching is high in this way, as shown in FIG.
As is apparent from the above, the processing temperature dependence of the etching rate is very large, the control of the conditions becomes complicated, and it is difficult to make the temperature of the sample uniform during processing. Not suitable for.

It should be noted that, here, almost the same results are obtained for the CoZrNb film and the Co film, respectively.
For elements other than Fe, Co and Ni such as Zr and Nb,
It is generally based on the fact that the vapor pressure of chloride is sufficiently higher than that of chlorides of Fe, Co and Ni. That is, F
When a magnetic thin film containing e, Co, and Ni as constituent elements is processed by RIE using a chlorine-based gas, Fe, Co,
Desorption / volatilization of Ni chloride limits the etching rate.

On the other hand, pure BCl ₃ or BCl ₃ --Cl
FIG. 4 shows the relationship between the processing temperature T and the etching rate with respect to the experimental result of processing the CoZrNb film by activating discharge of ₂ mixed gas. In the figure, the black triangle below, the black triangle above, the black square, and the black circle indicate the amount of gas introduced into the reaction chamber, respectively.
_{Cl 3 150sccm, BCl 3 80sccm-} Cl 2
_{60sccm, BCl 3 40sccm-Cl 2} 80sc
cm, BCl ₃ 20 sccm-Cl ₂ 90 sccm. In FIG. 4, the result of attempting to process the magnetic thin film by introducing a gas not activated by discharge into the reaction chamber without operating the capacitively coupled high frequency power supply is outlined (▽, Δ, □, ○) is also shown.

At this time, the activation energy Ea of etching is applied to the lower black triangle, upper black triangle, black square and black circle in the figure.
Are calculated to be about 0.35 eV and 0.38 eV, respectively.
V, 0.44 eV, and 0.50 eV, which are extremely low values with respect to the evaporation energy of CoCl ₂ of the reaction product of 1.24 eV due to the progress of physical etching due to the BC ions or radicals. Has become. In addition, ▽, △, □, and
In the case of ◯, the etching does not proceed, and it can be understood that the processing can be performed at a high etching rate practically sufficient even at a processing temperature of 300 ° C. or less where etching due to thermal reaction and thermal evaporation can be ignored. Furthermore, the etching activation energy E
Although a is the lowest under the black triangle in which BCl ₃ is used alone, the etching rate is higher when BCl ₃ -Cl ₂ mixed gas is used, and it is possible to process the magnetic thin film at a lower temperature and a higher speed. It is clear that the combined use of activated BCl ₃ and activated Cl ₂ is effective. [Experimental Example 2] Ni ₈₁ Fe ₁₉ film and Fe as magnetic thin film
For the sample on which the ₈₄ Si ₁₀ Al ₆ film was formed, BCl ₃ −
The amount of gas introduced into the reaction chamber was adjusted to BC by using Cl ₂ mixed gas.
The magnetic thin film was processed by RIE in exactly the same manner as in Experimental Example 1 except that the film was fixed at 40 sccm of 1 ₃ −80 sccm of Cl ₂ . As a result, the etching does not proceed using the gas that is not activated by the discharge, and the temperature range in which the etching due to the thermal reaction and the thermal evaporation can be ignored is Ni.
Fe film is about 400 ℃ or less, FeSiAl film is 300 ℃ or less
It was about the following. The activation energy Ea of etching is low at 0.75 eV for the NiFe film and 0.50 eV for the FeSiAl film, and the etching rate at 300 ° C. is about 100 nm / min.
The eSiAl film was about 500 nm / min, which was inferior to the case of the CoZrNb film shown in FIG. 4, but a practically sufficient value was obtained. Therefore, it was confirmed that the magnetic thin film containing any of Fe, Co and Ni as constituent elements can be anisotropically processed at low temperature and at high speed.

Further, the values of the etching rates obtained at this time are the values of Fe and Co between the CoZrNb film in Experimental Example 1 and the above-mentioned NiFe film and FeSiAl film.
Also, there is no difference as expected from the difference in evaporation energy or vapor pressure between the reaction products of Ni and chlorine-based gas. That is, the chlorides FeCl ₂ , CoCl ₂ , and Ni produced by the reaction of Fe, Co, and Ni with chlorine-based gas
The vaporization energies of Cl ₂ are 1.46 eV and
It is known to be 1.24 eV and 2.16 eV. Also, these FeCl ₂ , CoCl ₂ , and NiCl ₂
Vapor pressure around 300 ° C is 8 × 10 ^-3
Pa, 7 × 10 ⁻² Pa, 5 × 10 ⁻⁶ Pa, which are very different. Note that FIG. 5 shows vapor pressure curves of chlorides of Fe, Co, and Ni.

FeSiAl containing Fe as a constituent element
In the case of a membrane, it reacts with chlorine-based gas as shown in Fig. 3
FeCl ₃ (vaporization energy of about 1.32 eV) having a very high vapor pressure of about 4 × 10 ⁴ Pa at 00 ° C. was partially generated, and as a result, the etching rate was slightly improved. Conceivable. However, in this experimental example, the NiFe film having a Fe content of only 19 at% was processed at a higher etching rate than predicted from the evaporation energy and vapor pressure of NiCl _2. Cannot be discussed only by comparing the evaporation energies and vapor pressures of the Fe, Co, and Ni chlorides. Therefore, the improvement of the etching rate as described above is not based solely on the chemical mechanism such as the contribution of the generation of FeCl ₃ , but the promotion of the desorption of the reaction product by the physical etching is greatly involved. I was able to estimate. [Experimental Example 3] Here, Co ₈₇ Zr ₅ N was used as the magnetic thin film.
For the sample as shown in FIG. 2 with the b ₈ film formed,
The magnetic thin film was processed by RIE using BCl ₃ —Cl ₂ mixed gas. At this time, the CoZrNb film is processed by appropriately changing the discharge density P, the cathode drop voltage (discharge voltage) V, and the processing temperature T of the sample, and the etching rate, the mask etching selection ratio, the side etching ratio, Appropriate conditions were considered from the damage of residue, magnetic thin film, etc.

First, Cl in a BCl ₃ -Cl ₂ mixed gas was used.
_{When the} amount of ₂ is in the range of 40 to 85 vol%, if the gas pressure is kept constant, the cathode drop voltage V is uniquely determined if the discharge density P is determined even if the mixing ratio of BCl ₃ and Cl ₂ is changed. After confirming the above, the discharge density P and the processing temperature T are changed while maintaining the gas pressure at about 10 Pa, and CoZ
The rNb film was processed and evaluated. As a result, as a general tendency, when the discharge density P is increased, the etching rate can be improved and the side etching ratio can be reduced, and the generation of residues can be suppressed, while the selectivity ratio to the mask etching is lowered, and particularly When the discharge density P was extremely high, damage (roughness) due to heating due to excessive power input and incidence of excessive energy ions or radicals was observed in the mask, the magnetic thin film under the mask, and the underlying layer.

Specifically, if the discharge density P exceeds 10 W / cm ² , the damage can be detected by SEM observation.
^{At 2 and} above, the damage was significant. On the other hand, with respect to the mask etching selectivity, the discharge density P is 8 W / cm ² and the processing temperature T is 300 ° C. Even under the condition that it is difficult to secure the mask etching selectivity, the mask etching selectivity is about 2 which is a practically sufficient value. When the discharge density P was 2 W / cm ² and the processing temperature T was 300 ° C., a selectivity ratio to mask etching of 10 or more was obtained. The decrease in the selective ratio to the mask etching with the increase in the discharge density P is due to the increase in the ion sputtering phenomenon due to the increase in the cathode drop voltage V.

Furthermore, the side etching ratio, the mask etching selectivity and the generation of residues also depend on the processing temperature T. The lower the processing temperature T is, the side etching ratio is reduced and the mask etching selectivity is improved. Tended to occur. Further, when the discharge density P is less than 1 W / cm ² even in a temperature range of 100 ° C. or higher and 300 ° C. or lower where a practically sufficient etching rate can be obtained and etching due to thermal reaction and thermal evaporation can be ignored, the magnetic thin film Thermal reaction due to neutral radicals, etc. in the exposed area,
The thermal evaporation became dominant and the anisotropy of the processed shape was impaired, and a large amount of low chloride residue of low-grade chloride was generated. That is, from the above, the preferable discharge density P is 1
It became clear that it was within the range of -10 W / cm ² .

Next, the discharge density P is fixed near the critical value found here, and then the cathode drop voltage V is changed by changing the gas pressure in the reaction chamber, and CoZrN
The film b was processed and evaluated. First, the discharge density P is 10W
If set to / cm ^2, the cathode drop voltage V is 2.5kV becomes approximately 10Pa gas pressure, further cathode drop voltage V gas pressure 5Pa rose to 3 kV, this time working temperature T is 100 ° C. to 300 When the processing was performed under the condition of ℃ or less, the mask and the magnetic thin film under the mask were damaged due to the incidence of excessive energy ions or radicals. Therefore, the gas pressure is 20 Pa, the cathode drop voltage V
Is about 2 kV, the mask and the magnetic thin film under the mask are not particularly damaged, and the cathode drop voltage V is 2.5 kV.
It was revealed that the magnetic thin film is easily damaged when V is exceeded.

On the other hand, when the discharge pressure P was set to 1 W / cm ² and the gas pressure was changed, when the gas pressure was 7 to 15 Pa, the cathode drop voltage V was 0.7 to 0.55 kV and was incident on the surface to be processed. The ions or radicals to be processed have sufficient energy, and the anisotropy of the processed shape was good in the temperature range of the processing temperature T of 100 ° C. or higher and 300 ° C. or lower. However, when the gas pressure was increased to 25 Pa and the cathode drop voltage V was decreased to 0.38 kV, the energy was insufficient even though the density of the ions or radicals incident on the surface to be processed was sufficient, so the processing temperature T was set to about 300 ° C. Then, the side etching ratio was significantly increased, making it difficult to perform anisotropic processing. Next, while maintaining the gas pressure at 25 Pa, the discharge density P is increased and the cathode drop voltage V is set to 0.5 k.
When the temperature is increased to V, the side etching ratio is reduced to about 1/5 even under the condition that the processing temperature T is 300 ° C. and the anisotropy of the processed shape is likely to decrease. Further, when the cathode drop voltage V is 1 kV or more, the side etching ratio is increased. It became about 1/20 or less. Even if the cathode drop voltage V is not increased to 0.5 kV, it is possible to perform sufficient anisotropic processing by lowering the processing temperature T. However, the side etching is performed even when the processing temperature is about 300 ° C. The ratio is practically sufficient 1/5
In order to control below a certain level, the cathode drop voltage V is 0.5 kV
It has been found that processing under the above conditions is preferable. [Experimental Example 4] BCl ₃ -Cl ₂ mixed gas (BCl _3: 3
0 vol%, Cl ₂ : 70 vol%) and a deposition gas were appropriately introduced into the reaction chamber, the discharge density was set to 2 W / cm ² , the sample processing temperature was set to 300 ° C., and the gas pressure was set to 10 Pa. A magnetic thin film was processed by RIE on a sample as shown in FIG. 2 on which a Co ₈₇ Zr ₅ Nb ₈ film was formed. First, only the BCl ₃ —Cl ₂ mixed gas was introduced into the reaction chamber to process the CoZrNb film, and the processed shape was evaluated by observing a cross-sectional SEM image. The side etching ratio in the obtained pattern was 1/20. there were. Then, as a deposition gas, Si
Cl ₄ and O ₂ were mixed in the BCl ₃ —Cl ₂ mixed gas in an amount of 8 vol%, and similar processing and evaluation were performed. As a result, a processed shape in which side etching was hardly detected by cross-sectional SEM image observation was obtained.

Further, SiCl ₄ , O as a deposition gas is used.
Similar results were obtained even when TiCl ₄ and N ₂ were used instead of ₂ . When TiCl ₄ having a relatively low vapor pressure is used as the deposition gas, liquid TiCl ₄ contained in a bubbler is introduced into the reaction chamber by bubbling with a carrier gas. Furthermore, SiC
Even if l ₄ , O ₂ or N ₂ was used alone as a BCl ₃ —Cl ₂ mixed gas, side etching of the CoZrNb film was suppressed and the anisotropy of the processed shape could be increased.

[0058]

As described above in detail, according to the present invention, fine patterning is performed at a low temperature at a high speed and with high accuracy even on a magnetic thin film having a large material area and excellent material selectivity and economy. It is possible to provide a method of processing a magnetic thin film capable of processing.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an RIE experimental apparatus used for carrying out the present invention.

FIG. 2 is a cross-sectional view showing a structure of a sample used for carrying out the present invention.

FIG. 3 is a schematic diagram of a CoZrNb film and a Co film formed by introducing pure Cl ₂ .
The characteristic view which shows the experimental result at the time of processing a film.

FIG. 4 is a characteristic diagram showing an experimental result of processing a CoZrNb film by activating discharge of pure BCl ₃ or BCl ₃ —Cl ₂ mixed gas.

FIG. 5 is a characteristic diagram showing vapor pressure curves of Fe, Co, and Ni chloride.

[Explanation of symbols]

1 ... Reaction chamber, 21 ... Discharge cathode, 22 ... Sample stage, 3
...... Sample, 4 ...... Capacitive coupling type high frequency power source, 5 ...... Counter electrode, 61 ...... Gas supply source, 62 ...... Gas flow rate regulator, 6
3 ... Gas supply ring, 71 ... Sample heating infrared lamp, 72 ... Focus lamp housing surface, 73 ... Infrared transmitting quartz window, 8 ... Gas exhaust system, 9 ... Cathode drop voltage monitor, 10 ... Sample temperature monitor, 11 ... Gas pressure gauge, 31 ... Si substrate, 32 ... SiO ₂ sputtered film, 33
... magnetic thin film, 34 ... mask.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI H01L 21/3065 H01L 21/302 104Z (56) Reference JP-A-58-147124 (JP, A) JP-A-7-130572 ( JP, A) JP 4-129014 (JP, A) JP 7-233488 (JP, A) JP 8-23152 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23F 4/00 G11B 5/127 G11B 5/31 G11B 5/84 H01F 10/08 H01L 21/3065

Claims (12)

(57) [Claims] 1. A mask having a predetermined pattern is arranged on a magnetic thin film made of a magnetic material containing at least one of Fe, Co and Ni, and activated BCl ₃ is exposed on the exposed portion of the magnetic thin film. supplying a reactive gas containing,
By removing the magnetic thin film of the exposed portion 100 ° C. or higher 300 ° C. at a temperature by reacting with the magnetic material,
A method of processing a magnetic thin film, wherein desired patterning is performed on the magnetic thin film. 2. At least one of Fe, Co and Ni
Predetermined pattern on the magnetic thin film made of the contained magnetic material
A mask having a magnetic film on the exposed portion of the magnetic thin film.
Activated BCl ₃ Reactive Gas and SiC Containing
l _Four Alternatively, by supplying a deposition gas containing CO,
The magnetic thin film on the exposed part is removed by reacting with the magnetic material.
The desired patterning on the magnetic thin film.
Method of processing magnetic thin film. 3. The method for processing a magnetic thin film according to claim 2 , wherein the processing temperature is 100 ° C. or higher and 300 ° C. or lower. 4. The method for processing a magnetic thin film according to claim 1, wherein the reactive gas contains activated Cl ₂ . 5. Cl based on the total amount of BCl ₃ and Cl _2
The amount of ₂ is 0 to 90 vol%.
4. The method for processing a magnetic thin film described in 4 . 6. Cl with respect to the total amount of BCl ₃ and Cl _2.
The method for processing a magnetic thin film according to claim 4 , wherein the amount of ₂ is 40 to 85 vol%. 7. The reactive gas contains activated Cl ₂ .
And, mixing ratio claim 2 or 3 processing method of the magnetic thin film, wherein the a 5～30Vol% based on the total amount of BCl ₃ and Cl ₂ of the deposition gas. 8. The method for processing a magnetic thin film according to claim 1, wherein the reactive gas is diluted with a rare gas and supplied. 9. The method for processing a magnetic thin film according to claim 1, wherein the reactive gas containing BCl ₃ is activated by electric discharge. 10. The discharge density in the discharge is 1 to 10
The method for processing a magnetic thin film according to claim 9, wherein W / cm ₂ is set. 11. The cathode drop voltage in the discharge is set to 0.
The magnetic thin film processing method according to claim 9 or 10, wherein the voltage is set to 5 to 2.5 kV. 12. The gas pressure of the reactive gas is 5 to 50 P.
The magnetic thin film processing method according to claim 9, wherein the magnetic thin film is a.