JP4557144B2 - Manufacturing method of ceramics - Google Patents

Description

  The present invention relates to a method for manufacturing ceramics such as an oxide film, a nitride film, and a ferroelectric film, a manufacturing apparatus therefor, a semiconductor device using a ferroelectric film, and a piezoelectric element.

When forming a ferroelectric material such as PZT (Pb (Zr, Ti) O ₃ ) or SBT (SrBi ₂ Ta ₂ O ₉ ), a high process temperature is required. For example, a temperature of 600 to 700 ° C. is usually required for the PZT film formation, and a temperature of 650 to 800 ° C. is required for the SBT film formation. The characteristics of these ferroelectrics depend on their crystallinity, and generally the higher the crystallinity, the better.

  In a semiconductor device including a capacitor including a ferroelectric film (ferroelectric capacitor), for example, a ferroelectric memory device, the crystallinity of the ferroelectric has characteristics such as remanent polarization characteristics, coercive electric field characteristics, fatigue characteristics, and the like. Significantly affects imprint characteristics. In order to obtain a ferroelectric with good crystallinity, since the ferroelectric has a perovskite crystal structure having a multi-component system and a complicated structure, atoms require high migration energy. As a result, high process temperatures are required for ferroelectric crystallization.

  However, if the process temperature of the ferroelectric film is high, the ferroelectric memory device is likely to be damaged. That is, the ferroelectric material needs to be subjected to high temperature treatment in an oxygen atmosphere for crystallization. When the insulating layer is formed by oxidizing the polysilicon or the electrode material during the high temperature treatment, the characteristics of the ferroelectric capacitor are deteriorated by the insulating layer, and further, the transistor characteristics on the semiconductor side are deteriorated by heat. Further, Pb and Bi, which are constituent elements of PZT or SBT, are easily diffused, and these elements are deteriorated by diffusing to the semiconductor device side. Such deterioration becomes more prominent as the process temperature of the ferroelectric film is higher, and becomes more prominent as the semiconductor device is highly integrated (for example, a semiconductor device having a degree of integration of 1 Mbit or more).

  Therefore, at present, the ferroelectric capacitor is applied to a semiconductor device having an integration degree (for example, 1 to 256 kbit) that has a relatively small influence even when the process temperature of the ferroelectric film is high. However, at present, DRAM, flash memory, and the like already require a degree of integration from 16 M bits to G bits, which limits the field of application of ferroelectric memory devices. On the other hand, if the process temperature of the ferroelectric is lowered to prevent the deterioration of the device due to the high temperature oxygen atmosphere as described above, the crystallinity of the ferroelectric film is lowered. As a result, the remanent polarization characteristic of the ferroelectric capacitor is lowered, and the fat identification, imprint characteristic and retention characteristic are also lowered.

  An object of the present invention is to provide a manufacturing method and a ceramic manufacturing apparatus capable of obtaining ceramics having high characteristics such as crystallinity while lowering the process temperature.

  Another object of the present invention is to provide a semiconductor device and a piezoelectric element using ceramics obtained by the method of the present invention.

(A) 1st manufacturing method The 1st manufacturing method which concerns on this invention forms a ceramic film, supplying the active species of the substance used as a part of the raw material of ceramics, and electromagnetic waves to a predetermined area | region. Process.

  According to this manufacturing method, by irradiating the film with the active species and the electromagnetic wave, the migration energy of the film can be increased synergistically, and ceramics with excellent film quality can be formed. Furthermore, by supplying electromagnetic waves to the predetermined region, not only the migration energy of the active species is increased, but also the density of the active species can be increased. As a result, ceramics can be formed at a lower process temperature than when no active species and electromagnetic waves are supplied. For example, in the formation of a ferroelectric, a temperature lower than 600 ° C., more preferably 450 ° C. or lower can be applied.

  The above effects are the same in the present invention described below.

  The first manufacturing method further has the following aspects.

  (1) At least active species of a substance that becomes a part of a ceramic raw material, electromagnetic waves, and other reactive species of the ceramic raw material can be supplied to a predetermined region. In this manufacturing method, the crystallization can be performed simultaneously with the film formation of the ceramic.

  In this manufacturing method, as shown in FIG. 1, in order to form the ceramic film 20 on the substrate 10, an active species 100A, another reactive species 300A, and an electromagnetic wave 200A are supplied to the film formation region. . The ceramic film 20 is formed by the reaction between the reactive species 300A and the active species 100A. At this time, the electromagnetic wave 200A and the active species 100A have an effect of activating the reaction between the reactive species 300A and the active species 100A and further increasing the migration energy of atoms in the film. The active species 100A, the electromagnetic wave 200A, and the reactive species 300A are selected depending on the composition of the ceramic to be obtained, the crystal structure, the purpose of use of the ceramic material, and the like.

  The active species 100 </ b> A is generated by the active species supply unit 100, the reactive species 300 </ b> A is supplied via the reactive species supply unit 300, and the electromagnetic wave 200 </ b> A is supplied by the electromagnetic wave generation unit 200.

  (2) A film made of a substance that becomes a part of the raw material of the ceramic can be formed in the predetermined region. In this manufacturing method, the crystallization can be performed simultaneously with the film formation of the ceramic, as in the manufacturing method of (1) above. However, this manufacturing method differs from the manufacturing method of (1) above in that a part of the ceramic raw material is deposited.

  In this manufacturing method, as shown in FIG. 2, a film 20 a made of a substance that becomes a part of a ceramic raw material is formed on a substrate 10. Then, by supplying the active species 100A to the predetermined region by the active species supply unit 100 and the electromagnetic wave 200A by the electromagnetic wave generator 200, the film 20a and the active species 100A are reacted to form a ceramic film. At this time, the electromagnetic wave 200A and the active species 100A have an effect of activating the reaction between the film 20a and the active species 100A and further increasing the migration energy of atoms in the film.

  (3) A step of supplying active species and electromagnetic waves to the first ceramic film to form a second ceramic film having a crystal structure different from that of the first ceramic can be included. According to this manufacturing method, the pre-formed ceramic film is crystallized.

  In this manufacturing method, as shown in FIG. 2, the active species 100A is supplied to the first ceramic film 20c on the substrate 10 by the active species supply unit 100 and the electromagnetic wave 200A is supplied by the electromagnetic wave generation unit 200. The migration energy of atoms in one ceramic film 20c is increased, and a second ceramic film with high crystallinity can be formed.

  The first ceramic is preferably a ceramic having an amorphous state or low crystallinity. By irradiation with the active species 100A and the electromagnetic wave 200A, such a first ceramic film becomes a second ceramic having high crystallinity due to an increase in atom migration energy in the film.

  The effects of the first manufacturing method described above are the same in other manufacturing methods according to the present invention.

  In the present invention, the ceramic film or the second ceramic film preferably has a thickness of 5 to 30 nm. When the thickness of the film is within this range, the effect of increasing the migration energy of atoms by the electromagnetic wave and the active species can be obtained in the entire film. If the thickness of the film is less than 5 nm, the composition of the film tends to vary. On the other hand, if the thickness of the film is larger than 30 nm, it is difficult to obtain the effect of increasing the migration energy of atoms in the entire film.

(B) Second Manufacturing Method According to the second manufacturing method of the present invention, the step of forming the ceramic thin film having a predetermined thickness by applying the first manufacturing method described above is repeated a plurality of times. A ceramic film having a predetermined thickness can be manufactured. Such a manufacturing method has the following aspects.

  (1) Similarly to (A) and (1) above, a ceramic film having a predetermined thickness is formed while supplying at least one of active species of a substance that becomes at least a part of ceramic raw materials and electromagnetic waves to a predetermined region. The process can be repeated a plurality of times to form a film having a predetermined thickness.

  (2) Similarly to the above (A) and (2), a film made of a substance that becomes a part of the ceramic raw material can be formed in the predetermined region.

  (3) The first step of forming the first ceramic film, and at least one of active species and electromagnetic waves is supplied to the first ceramic film in the same manner as in the above (A) and (3), And a second step of forming a second ceramic film having a different crystal structure, the first and second steps can be alternately performed to form a film having a predetermined thickness.

  In this manufacturing method, as shown in FIG. 3, the first ceramic film 20 a is formed on the substrate 10 in the film forming apparatus 2000. Next, the substrate 10 on which the first ceramic film 20a is formed is transferred to the crystallization apparatus 1000. In the crystallization apparatus 1000, the active species 100A from the active species supply unit 100 and the electromagnetic wave 200A from the electromagnetic wave generation unit 200 are supplied to the first ceramic film 20a, and the first ceramic film 20a is crystallized to the second. The ceramic film 20 is formed. The above film formation and crystallization steps are repeated.

  Also in this second manufacturing method, it is desirable that the thickness of the ceramic film or the second ceramic film is 5 to 30 nm, as in the first manufacturing method.

(C) Third Manufacturing Method In this manufacturing method, the formation region of the ceramic film is not the entire surface of the substrate, but a partial region, that is, a minute region. This manufacturing method has the following aspects.

(1) The formation region of the ceramic film is partial with respect to the substrate,
The method may include a step of forming a ceramic film while supplying at least one of active species of a substance that becomes at least a part of a raw material of ceramics and electromagnetic waves to a predetermined region.

  (2) In the same manner as (A) and (2) described above, a film made of a substance that becomes a part of the ceramic raw material can be formed in the predetermined region.

(3) The formation region of the ceramic film is partial with respect to the substrate,
A step of forming a second ceramic film having a crystal structure different from that of the first ceramic while supplying at least one of active species and electromagnetic waves to the first ceramic film can be included.

  (4) The following method is preferable as a method of partially forming the ceramic film on the substrate. That is, on the surface of the substrate, a film forming part having affinity for the ceramic to be formed and a non-film forming part having no affinity for the ceramic to be formed are formed in a self-aligning manner. A step of forming a ceramic film on the film forming portion.

(D) Another aspect of the production method according to the present invention The production method of the present invention may take the following aspects.

  (1) The active species of the substance that becomes a part of the raw material of the ceramic is a radical or ion obtained by activating a substance containing oxygen or nitrogen. That is, as the active species, an oxygen radical, ion or ozone can be used in the case of an oxide, and a nitrogen radical or ion can be used in the case of a nitride. As a method for generating radicals or ions, a known method, for example, an active species generating method using RF (radio frequency), microwave, ECR (electron cycloton resonance), ozoner, or the like can be exemplified.

  The electromagnetic wave is selected depending on the ceramic composition, reactive species, active species, and the like. A source such as an excimer laser, a halogen lamp, or a young laser (harmonic) can be used as the electromagnetic wave. Further, if an electromagnetic wave that can dissociate oxygen or nitrogen is selected, the concentration of active species can be increased.

  (2) In addition to the active species, radicals or ions obtained by activating an inert gas (xenon or argon) can be supplied to a predetermined region. For example, when xenon is used, its concentration increases in the generation of oxygen active species (oxygen radicals) using microwaves.

(E) Manufacturing apparatus according to the present invention The manufacturing apparatus of the present invention may take the following aspects.

  (1) An arrangement part of a substrate on which ceramics are formed, a heating part, an active species supply part for supplying active species of a substance that is at least a part of the raw material of the ceramic, and an electromagnetic wave generation for supplying electromagnetic waves And at least one of active species and electromagnetic waves can be supplied to the ceramic formation region.

  (2) The manufacturing apparatus according to (1) may further include a film made of a substance that is a part of a ceramic raw material or a film forming apparatus for forming a ceramic film in the same chamber.

(3) An arrangement part of a substrate on which ceramics are formed, a heating part, an active species supply part for supplying active species of a substance that is at least a part of ceramic raw materials, and an electromagnetic wave generation for supplying electromagnetic waves A crystallization apparatus capable of supplying at least one of active species and electromagnetic waves to a ceramic formation region,
The crystallization apparatus and a film forming apparatus comprising a separate chamber can be included.

  (4) In the manufacturing apparatus of (3), a load lock device may be provided between the crystallization device and the film forming device.

  (5) In the manufacturing apparatus of the above (1) to (4), the arrangement part of the base body may constitute the heating part.

  (6) In the manufacturing apparatus of (1) to (5) above, at least one of the active species supply unit and the electromagnetic wave generation unit can partially supply at least one of active species and electromagnetic waves to the base.

  (7) In the manufacturing apparatus of (1) to (6) above, at least one of the active species and the electromagnetic wave can be supplied in a state of moving relative to the substrate.

  (8) In the manufacturing apparatus of (3), the film forming apparatus can perform film formation by a coating method, an LSMCD method, a CVD method, or a sputtering method.

  (9) In the manufacturing apparatus of (2), the film forming apparatus can perform film formation by the LSMCD method or the CVD method.

  (F) The ceramic obtained by the manufacturing method according to the present invention is used for various applications. The following are typical applications.

  (1) A semiconductor device having a capacitor including a dielectric film formed by the manufacturing method of the present invention. As such a semiconductor device, there is a DRAM or a ferroelectric memory (FeRAM) device using a paraelectric material obtained by the manufacturing method of the present invention as a dielectric film.

  (2) A piezoelectric element including a dielectric film formed by the manufacturing method of the present invention.

[First Embodiment]
FIG. 4 is a diagram schematically showing a ceramic manufacturing method and a manufacturing apparatus according to the present embodiment. The manufacturing apparatus shown in FIG. 4 includes a film forming apparatus 2000, a crystallization apparatus 1000, and a load lock apparatus 3000. The object 30 is disposed so as to be capable of reciprocating between the film forming apparatus 2000 and the crystallization apparatus 1000 via the load lock apparatus 3000.

  The film forming apparatus 2000 is not particularly limited as long as it is an apparatus for forming the first ceramic film 20a on the substrate 10. In this embodiment, an LSMCD device capable of LSMCD (Liquid Source Missed Deposition) is used. The film forming apparatus 2000 includes a raw material tank 410 in which a ceramic material such as an organic metal is accommodated, a mist forming unit 420 that mists the raw material, a gas supply unit 430 that supplies a carrier gas, and the misted raw material and gas. And a raw material supply unit 450 for supplying a predetermined region on the substrate 10 placed on the placement unit (arrangement unit) 40. A mesh 460 is provided at the tip of the raw material supply unit 450. Further, a mask 470 for making the first ceramic film 20a to be formed into a predetermined pattern is disposed between the base 10 and the raw material supply unit 450 as necessary. The mounting unit 40 includes a heating unit for heating the base 10 to a predetermined temperature.

  According to the film forming apparatus 2000, the first ceramic film 20a is formed by the following procedure.

  First, the raw material supplied from the raw material tank 410 to the mist forming unit 420 becomes a mist having a diameter of 0.1 to 0.2 μm, for example, by ultrasonic waves. The mist formed by the mist forming unit 420 and the gas supplied from the gas supply unit 430 are sent to the raw material supply unit 450. Then, the raw material seed 300 </ b> A is supplied from the raw material supply unit 450 toward the base body 10, and the amorphous first ceramic film 20 a is formed on the base body 10.

  When an organic metal is used as a raw material, the amorphous first ceramic film 20a is obtained by heating the substrate 10 to decompose (so-called degreasing) the organic metal complex. This degreasing may be performed in a separate room using RTA or furnace.

  The first ceramic film 20a formed by using the LSMCD method is advantageous in crystallization because it has a fine and moderate distribution of depletion within the film, and thus has a state in which atoms are likely to migrate. The first ceramic film 20a is preferably formed with a thickness of, for example, 5 to 30 nm in order to effectively perform crystallization in the next crystallization step. Since the thickness of the first ceramic film 20a is within this range, as described above, the crystallization treatment does not cause variation in composition, the crystal grain size can be reduced, and the ceramic has high crystallinity. Can be obtained.

  The crystallization apparatus 1000 includes an active species supply unit 100 and an electromagnetic wave generation unit 200. The active species 100 </ b> A formed by the active species supply unit 100 is supplied to a predetermined region of the substrate 10 through the supply path 110. In addition, the electromagnetic wave 200A generated by the electromagnetic wave generation unit 200 is also irradiated to the region to which the active species 100A is supplied. The arrangement of the active species supply unit 100 and the electromagnetic wave generation unit 200 is appropriately set so as not to prevent the supply of the active species 100A and the electromagnetic wave 200A.

  In the crystallization apparatus 1000, the first ceramic film 20a in the amorphous state formed by the film formation apparatus 2000 is irradiated with the active species 100A and the electromagnetic wave 200A, whereby atoms migrate in the first ceramic film 20a. Energy increases. As a result, crystallization is performed at a relatively low temperature, specifically at a temperature lower than 600 ° C., more preferably at a temperature of 450 ° C. or lower, and the second ceramic film 20b having high crystallinity is formed.

  The formation of the first ceramic film 20a in the film forming apparatus 2000 and the formation of the crystalline ceramic film 20c in the crystallization apparatus 1000 may be repeated a plurality of times in order to obtain a ceramic film having a predetermined thickness. it can.

  In particular, when depositing SBT, since SBT is a layered perovskite, the growth rate varies depending on the crystal orientation, and as a result, it is easy to form grooves and holes that are not desirable in polycrystals. However, by repeatedly laminating thin films as in the present embodiment, a homogeneous film can be obtained in a state where the grooves and holes described above are filled.

  According to the present embodiment, by using the LSMCD method in the film forming apparatus 2000, it is possible to obtain the first ceramic film 20a in a state where atoms are likely to migrate due to fine and appropriate depletion. In the crystallization apparatus 1000, by irradiating the first ceramic film 20a with the active species 100A and the electromagnetic wave 200A, a large migration energy can be imparted to the atoms. As a result, the first ceramic film 20a is better at a lower temperature than the conventional apparatus. Crystallization can be performed.

[Second Embodiment]
FIG. 5 is a diagram schematically showing a film forming apparatus 4000 according to the present embodiment. The film formation apparatus 4000 is an example of an apparatus that can perform film formation and film crystallization at the same time. In this embodiment mode, film formation is performed by the MOCVD method, which is combined with the crystallization method of the present invention.

  The film forming apparatus 4000 includes a raw material tank 510, a mist forming unit 520, a heater 540, and a raw material supply unit 550 as a system for supplying the raw material. Since the raw material tank 510 and the mist making unit 520 are the same as the raw material tank 410 and the mist making unit 420 described in the first embodiment, description thereof is omitted. The heater 540 heats and vaporizes the misted raw material. Then, from the raw material supply unit 550, the reactive species 300A is supplied to a predetermined region of the base 10.

  Above the mounting table 40, the active species supply unit 100 and the electromagnetic wave generation unit 200 are disposed at a position that does not hinder the supply of the reactive species 300 </ b> A. The active species supply unit 100 irradiates a predetermined region of the base 10 with the active species 100A, and the electromagnetic wave generation unit 200 irradiates the electromagnetic wave 200A.

  The wavelength of the electromagnetic wave is preferably 193 to 300 nm when an oxide such as PZT or SBT is formed. When electromagnetic waves of this wavelength are used, atomic migration in the oxide is enhanced. Further, when 193 nm ArF is used as an electromagnetic wave, oxygen can be dissociated and the concentration of active species can be increased.

  According to film forming apparatus 4000 according to the present embodiment, a ceramic film is formed by MOCVD, and at the same time, the film is crystallized by active species 100A and electromagnetic wave 200A to form ceramic film 20. In the film formation apparatus 4000, by irradiating the ceramic film with the active species 100A and the electromagnetic wave 200A simultaneously with the film formation, a large migration energy can be imparted to the atoms. As a result, it is better at a lower temperature than the conventional apparatus. Crystallization can be performed.

[Third Embodiment]
FIG. 6 is a diagram illustrating an example of a method for supplying the active species 100A and the electromagnetic wave 200A. In the present embodiment, at least one of the active species 100 </ b> A and the electromagnetic wave 200 </ b> A, preferably both or at least the electromagnetic wave 200 </ b> A is partially supplied to the ceramic formation region of the workpiece 30.

  Specifically, the active species 100A and the electromagnetic wave 200A are supplied to the line-shaped region 30a or the spot-shaped region 30b as shown in FIG. The regions 30 a and 30 b to which the active species 100 </ b> A and the electromagnetic wave 200 </ b> A are supplied are set so that they can move relative to the object 30. In order to move the regions 30a and 30b relative to the object 30 to be processed, any of a method of moving the object 30 to be processed, a method of moving the regions 30a and 30b, and a method of moving both of them may be used. In order to move the regions 30a and 30b relative to the object 30 to be processed, when the active species 100A and the electromagnetic wave 200A are supplied in a line shape, at least one of them is orthogonal to the line-shaped region. When the active species 100A and the electromagnetic wave 200A are supplied in the form of spots, at least one of them is in one direction (for example, the X direction or the Y direction in FIG. 6). Moved.

  Since the regions 30a and 30b to which at least one of the active species 100A and the electromagnetic wave 200A is supplied are partial, the temperature of the object 30 can be reduced while suppressing the temperature increase of the object 30 to be processed. The strength of energy and electromagnetic wave 200A can be increased.

  When the strength of the electromagnetic wave 200A is increased, the temperature of the object to be processed 30 increases, so that depending on the type of the object to be processed 30, damage may be caused by heat. For example, in the case where a semiconductor device is formed on the substrate of the object 30 to be processed, it is conceivable that an oxide film is formed or the MOS element is damaged due to diffusion of impurities, leading to deterioration of the semiconductor device. However, according to this Embodiment, the temperature rise of the to-be-processed object by irradiation of electromagnetic waves can be suppressed by making the area | regions 30a and 30b partial.

  The intensity of the electromagnetic wave 200A and the energy of the active species 100A are set in consideration of the temperature rise of the object to be processed, the ceramic composition, and the like.

[Fourth Embodiment]
7A and 7B show a modification of the film forming method of the present invention. FIG. 7A shows a plan view of the substrate 10, and FIG. 7B shows a cross section taken along the line AA in FIG. 7A.

  In the present embodiment, an example in which ceramic is partially formed on the substrate 10 is shown. Since the ceramic film is partially formed in this way, the capacity of the portion that needs to be heated is relatively small compared to the case where the ceramic is entirely formed. Can be reduced. As a result, the temperature of the heating process can be relatively lowered. Therefore, according to this embodiment, in addition to the decrease in the process temperature due to the supply of active species and electromagnetic waves, a further decrease in the process temperature can be achieved.

  In the present embodiment, the substrate 10 includes a first substrate 12 and a film forming unit 14 and a non-film forming unit 16 formed on the first substrate 12.

  The film forming unit 14 is made of a material having high chemical or physical affinity with the ceramic formed on the substrate 10, for example, a material having good wettability with respect to a ceramic raw material or reactive species. On the other hand, the non-film forming part 16 has a poor chemical or physical affinity with the ceramic to be formed, and is formed of, for example, a material having low wettability with respect to the ceramic raw material or reactive species. By configuring the surface of the substrate 10 in this way, the ceramic film 20 having a predetermined pattern is formed by disposing the film forming portion 14 in a region where the ceramic film is to be formed.

  For example, when a ferroelectric film is formed as the ceramic film, iridium oxide can be used as the material of the film forming portion 14 and a fluorine-based compound can be used as the material of the non-film forming portion 16.

  The method for producing a ceramic according to the present embodiment can be applied to various ceramics including a ferroelectric, but can be suitably used particularly for a layered perovskite. In the layered perovskite, oxygen, particularly radicals (atomic oxygen), is likely to diffuse in the direction perpendicular to the C axis, and therefore, radical migration from the side surface of the ceramic film 20 is easily performed in the heating process for crystallization. . As a result, oxygen vacancies in the perovskite are reduced, the polarization characteristics are improved, and deterioration of the fateg characteristics and imprint characteristics is suppressed.

[Fifth Embodiment]
FIG. 8 shows an example of a semiconductor device (ferroelectric memory device 5000) using a ferroelectric obtained by the manufacturing method according to the present invention.

  The ferroelectric memory device 5000 has a CMOS region R1 and a capacitor region R2 formed on the CMOS region R1. The CMOS region R1 has a known configuration. That is, the CMOS region R1 includes the semiconductor substrate 1, the element isolation region 2 and the MOS transistor 3 formed on the semiconductor substrate 1, and the interlayer insulating layer 4. The capacitor region R2 includes a capacitor C100 composed of the lower electrode 5, the ferroelectric film 6 and the upper electrode 7, a wiring layer 8a connected to the lower electrode 5, a wiring layer 8b connected to the upper electrode 7, And an insulating layer 9. The impurity diffusion layer 3a of the MOS transistor 3 and the lower electrode 5 constituting the capacitor C100 are connected by a contact layer 11 made of polysilicon or a tungsten plug.

  In the ferroelectric memory device 5000 according to the present embodiment, the ferroelectric (PZT, SBT) film 6 constituting the capacitor C100 has a temperature lower than that of a normal ferroelectric, for example, 500 ° C. or less in the case of PZT. In the case of SBT, it can be formed at a temperature lower than 600 ° C. Therefore, since the occurrence of damage to the CMOS region R1 due to heat can be suppressed, the capacitor C100 can be applied to a highly integrated ferroelectric memory device. Since the ferroelectric (PZT, SBT) film 6 can be formed at a temperature lower than that of a normal ferroelectric, the wiring layer (not shown) in the CMOS region R1 and the electrode portions 5 and 7 constituting the capacitor C100 are formed. Even if an expensive material such as iridium or platinum is not used as the material, there is no deterioration of the wiring or the electrode part. Therefore, an inexpensive aluminum alloy can be used as the material for these wiring layers and electrode portions, and the cost can be reduced.

  Further, in a semiconductor device such as a CMOS, the semiconductor process and the capacitor process are usually separated in order to prevent contamination by the ferroelectric (PZT, SBT). However, according to the manufacturing method of the present invention, the process temperature of the ferroelectric can be lowered, so that the capacitor can be continuously formed after the multilayer wiring process which is the final process of the normal semiconductor process. Therefore, the number of processes for isolation can be reduced, and the process can be simplified. Furthermore, since the manufacturing method of the present invention does not require isolation between the semiconductor process and the capacitor process, it is advantageous for manufacturing a semiconductor device in which logic, analog, and the like are mixedly mounted.

  The dielectric formed by the manufacturing method of the present invention is not limited to the ferroelectric memory device described above, and various semiconductor devices, for example, DRAMs, use a high dielectric constant paraelectric material such as BST to increase the size of the capacitor. Capacity can be increased.

  The dielectric formed by the manufacturing method of the present invention can be applied to other uses, for example, a piezoelectric body of a piezoelectric element used for an actuator.

  Furthermore, the nitride (silicon nitride, titanium nitride) formed by the manufacturing method of the present invention can be applied to, for example, a passivation film of a semiconductor device, a local interconnector film, and the like.

It is a figure which shows typically an example of the manufacturing method of this invention. It is a figure which shows typically an example of the manufacturing method of this invention. It is a figure which shows typically an example of the manufacturing method of this invention. It is a figure which shows typically 1st Embodiment which concerns on the manufacturing method and manufacturing apparatus of this invention. It is a figure which shows typically 2nd Embodiment which concerns on the manufacturing method and manufacturing apparatus of this invention. It is a figure which shows typically 3rd Embodiment which concerns on the manufacturing method and manufacturing apparatus of this invention. It is a figure which shows typically 4th Embodiment which concerns on the manufacturing method and manufacturing apparatus of this invention. It is a figure which shows typically the semiconductor device which concerns on the 5th Embodiment of this invention.

Explanation of symbols

10 substrate, 12 first substrate, 14 film forming part, 16 non-film forming part,
20 ceramic film, 100 active species supply unit, 100A active species,
200 Electromagnetic wave generator, 200A Electromagnetic wave, 1000 Crystallizer,
2000, 4000 Film forming device, 5000 ferroelectric memory device,
1 Semiconductor substrate, 3 MOS transistor, 5 Lower electrode, 6 Ferroelectric film,
7 Upper electrode, C100 capacitor, R1 CMOS region, R2 capacitor region

Claims (23)

At least a portion of the ceramic raw material substances active species, an electromagnetic wave, while supplying a predetermined area, seen including a step of forming a ceramic film,
A method for producing ceramics , wherein the ceramic film is crystallized at the same time as the ceramic film is formed . In claim 1,
A method for producing ceramics, wherein a film made of a substance that becomes a part of ceramic raw materials is formed in the predetermined region. In claim 1 or 2,
The method for producing ceramics, wherein the active species of the substance that is a part of the ceramic raw material is a radical, ion, or ozone obtained by activating a substance containing oxygen or nitrogen. In any one of Claims 1-3,
In addition to the active species, a method for manufacturing ceramics, further comprising supplying ions obtained by activating an inert gas to a predetermined region. In any one of Claims 1-4,
The method for producing ceramics, wherein the ceramic film has a thickness of 5 to 30 nm. Membrane having at least the active species that become part material of the ceramic raw material, an electromagnetic wave, while supplying a predetermined area, a step of forming a ceramic film having a predetermined thickness, carried out repeatedly a plurality of times, a predetermined thickness Form the
A method for producing ceramics , wherein the ceramic film is crystallized at the same time as the ceramic film is formed . In claim 6,
A method for producing ceramics, wherein a film made of a substance that becomes a part of ceramic raw materials is formed in the predetermined region. In claim 6 or 7,
The method for producing ceramics, wherein the ceramic film has a thickness of 5 to 30 nm. In any one of Claims 6-8,
The method for producing ceramics, wherein the ceramic film is partially formed on a substrate. In any one of Claims 6-9,
The method for producing ceramics, wherein the active species of the substance that is a part of the ceramic raw material is a radical, ion, or ozone obtained by activating a substance containing oxygen or nitrogen. In any one of Claims 6-10,
In addition to the active species, a method for manufacturing ceramics, further comprising supplying ions obtained by activating an inert gas to a predetermined region. The formation region of the ceramic film is partial to the substrate,
At least a portion of the ceramic raw material substances active species, an electromagnetic wave, while supplying a predetermined area, seen including a step of forming a ceramic film,
A method for producing ceramics , wherein the ceramic film is crystallized at the same time as the ceramic film is formed . In claim 12,
A method for producing ceramics, wherein a film made of a substance that becomes a part of ceramic raw materials is formed in the predetermined region. In claim 12 or 13,
On the surface of the substrate, a film forming part having an affinity for the ceramic to be formed and a non-film forming part having no affinity for the ceramic to be formed are formed in a self-aligning manner. A method for producing ceramics, comprising a step of forming a ceramic film in a film forming part. In claim 12 or 13,
The method for producing ceramics, wherein the active species of the substance that is a part of the ceramic raw material is a radical, ion, or ozone obtained by activating a substance containing oxygen or nitrogen. In claim 15,
The method for producing ceramics, wherein the active species is a radical or an ion obtained by activating a substance containing oxygen or nitrogen. In any one of Claims 12-16,
In addition to the active species, a method for manufacturing ceramics, further comprising supplying ions obtained by activating an inert gas to a predetermined region. In any one of Claims 12-17,
The method for producing ceramics, wherein the ceramic film has a thickness of 5 to 30 nm. In any one of Claims 12-18,
The method for producing ceramics, wherein the step of forming the ceramics is repeated a plurality of times. In any one of Claims 1-19,
The method for producing ceramics, wherein at least one of the active species and the electromagnetic wave is partially supplied to a substrate. In claim 20,
The method for producing ceramics, wherein at least one of the active species and the electromagnetic wave is supplied in a state of moving relative to the substrate. In any one of Claims 1-21,
The method for producing ceramics, wherein the ceramic film is made of a ferroelectric. In any one of Claims 1-22.
The ceramic film is formed at a temperature lower than 600 ° C.

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