JP2006140395A - Semiconductor memory and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phase change type nonvolatile memory which can be stable in characteristic from the beginning of rewriting and can have small variations in characteristic between elements, by initially crystallizing in the vicinity of a phase change material in an element fabricating process without causing any destruction such as delamination. <P>SOLUTION: The average width of a cross section parallel to the crystalline grain film surface is smaller than the maximum width of the contact area of one of electrodes at both sides of a phase change film having a smaller maximum width. The composition of chalcogenide phase change film is combined with the phase change film so that the crystal shape of the first-mentioned phase change film is not largely changed through a process of 400°C after initially crystallized. Upon the initial crystallization, the surface of the phase change film is protected by a thin electrode material layer or an insulator layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a semiconductor memory and a manufacturing method thereof, and more particularly to a phase change nonvolatile memory and a phase change transistor and a manufacturing method thereof.

A phase change memory (PCRAM) that has been researched and developed as a next-generation memory that integrates the advantages of each existing memory is a phase change type nonvolatile memory disclosed in, for example, Patent Document 1 and Patent Document 2, and includes OUM ( It is also called Ovonic Unified Memory).
The phase change memory uses a phase change material for the memory holding unit, and identifies and holds information by a difference in electric conductivity generated in each phase of a crystalline phase and an amorphous phase. As a feature, even if the phase change material is made relatively fine, the memory retention performance does not deteriorate. The two phases can also have orders of magnitude different electrical conductivity, and intermediate levels, i.e. multivalued, are possible. It is possible to select a phase change material that is advantageous for high-speed switching, and it has the potential as an ideal memory such as non-volatility, high bit density, and high-speed access.
According to the disclosed technology, a phase change memory has a basic memory cell (1 bit) in which a MOS transistor is connected to a minute phase change material cell, and a pulse current is applied to the phase change material for recording and erasing information. It is carried out by self-heating by the Joule heat that is generated. During recording, the phase change material is crystallized by applying a pulse current (set pulse) that heats the phase change material to a temperature range where the phase change material is relatively low temperature and the crystallization speed is high. At the time of erasing, a pulse current (reset pulse) is applied so that the phase change material is rapidly cooled after being heated to make the phase change material amorphous. The crystalline phase has a high electrical conductivity, and the amorphous phase has a relatively low electrical conductivity. During reproduction, information is read by applying a low voltage to the phase change material and converting the flowing current to a voltage.
FIG. 16 shows an example of the basic structure of the memory cell of the phase change memory. The phase change memory has a structure in which a MOS transistor (not shown), a silicon oxide insulating layer 32, a lower electrode 34, a phase change material 31 and an upper electrode 33 are sequentially stacked on a silicon substrate (not shown).

  On the other hand, as a phase change transistor, the one reported by Mr. Hosaka of Gunma University at Phase Change Symposium 2003 is known (see Non-Patent Document 1). As in the case of the phase change memory, the memory effect is exhibited by crystallizing or amorphizing the phase change film.

Japanese National Patent Publication No. 11-514150 JP-T-2001-502848 S. Hosaka, K. Miyauchi, T. Tamura, Y. Yin and H. Sone: “Proposal of memory transistor using a phase change and nano-size effects for high density memory array: Proceeding PCOS2003 (Proc. PCOS2003), Shizuoka (Shizuoka) ", (Japan), 2003, p.52-55 F. Pellizzer et al .: “2004 Symposium on VLSI Technology Digest of Technical Papers”, IEEE, 2004, p.18-19

In the manufacturing process, the phase change film, which is an information holding (memory) part, is crystallized during film formation by conventional heating, or alternatively, after film formation, it is heated and crystallized in the memory element manufacturing process. ing. However, in the former substrate heating film formation, the substrate temperature at which the surface can be formed without roughening is limited to a narrow temperature range around 100 ° C., and the margin is very narrow and the temperature control is difficult. Further, as shown in the example in FIG. 17, large non-uniform crystal grains are formed. Further, heating during the latter post-film formation process forms large crystal grains, and many minute gaps are formed between the crystal grains and the electrode or insulator layer, so that the adhesiveness is lowered and peeling is likely to occur. There was a bug. Furthermore, in both the substrate heating film formation and the post-film formation process, the crystallization state was different at the center and the edge of the substrate (silicon wafer) and lacked uniformity. In particular, the edge portion was poorly crystallized, and electrical properties were not obtained, making it difficult to use. In crystallization by heating during substrate heating and post-deposition processes, the crystal form is very different from the crystal form at the time of memory rewriting, and the phase change film has a large specific resistance at the stage where the number of rewrites is small and stable from the first time. There was also a problem that the recorded record could not be obtained. Further, since the crystal grain size is approximately the same as or larger than the size of the lower electrode, the characteristics differ depending on where the lower electrode is formed in the crystal grains, causing variations in characteristics between elements.
The object of the present invention is to perform initial crystallization without causing breakage such as delamination in the vicinity of the phase change material during the device manufacturing process, and the phase change type non-volatile that has stable characteristics from the beginning of rewriting and small variations in characteristics between devices. Is to provide memory.

  In order to achieve the above object, the cross-section perpendicular to the film surface is larger than the maximum width of the contact area of the electrode on either side of the film, the maximum contact area of which is in direct or indirect contact with the phase change film. The phase change film has a small average width of crystal grains when cut parallel to the film surface at the center in the film thickness direction. Indirect contact means contact through a thin insulating layer or conductive layer having a thickness of 20 nm or less. This is combined with the composition of a chalcogenide phase change film in which the crystal form does not change greatly in the process at 400 ° C. after the initial crystallization. The surface is protected with a thin conductive material layer or insulator layer during initial crystallization. Initial crystallization is performed under specific conditions at a higher temperature and shorter time than electric furnace heating.

  For example, in Non-Patent Document 2, the contact portion between the electrode (heater) and the phase change film is elongated, but if the crystal grain is larger than the smaller width but smaller than the larger width, the influence of the crystal grain is averaged. Therefore, variation in characteristics between elements can be prevented.

The laser crystallization apparatus has a high-power laser, a laser head that irradiates the silicon wafer with laser light emitted from the laser, and a transport mechanism that moves the silicon wafer in at least one direction, and irradiates the silicon wafer. The laser crystallization apparatus is capable of irradiating pulsed light with a laser spot area of 10 ⁻⁶ cm ² or more and 10 ⁻³ cm ² or less and 100 ns or more and 1 second or less. According to the above apparatus, high-density and appropriate irradiation energy can be applied to the phase change material of the phase change memory, and the entire phase change material of the phase change nonvolatile memory can be uniformly crystallized. Further, according to the above apparatus, only the phase change material can be heated to the crystallization temperature in a short time, and the laminated film in the vicinity of the phase change material can be set in a set state without causing thermal damage due to volume change. The above-mentioned object can be achieved.
The same applies to the phase change film of the phase change transistor.

  Peeling during the process induced by crystallization can be prevented. The crystal structure of the initial crystallized state and the set state are close, and the characteristics are stable from the beginning of rewriting. Variations between elements due to large crystal grains can be reduced.

Hereinafter, embodiments according to the present invention will be described in detail with reference to the drawings.
<Example 1>
FIG. 1 is a fragmentary cross-sectional view of a semiconductor integrated circuit device according to Embodiment 1 of the present invention. FIG. 1 is a cross-sectional view of a memory cell area of a logic embedded memory, a logic logic circuit area, and a phase change memory cell. Of these areas, lgc is referred to as a logic circuit area. In this logic circuit region lgc, an n-channel type MISFET QN is formed. The n-channel type MISFET QN is formed on the p well 2 so as to be spaced apart from each other, and has an LDD (Lightly Doped Drain) structure, a gate insulating film 4 formed on the semiconductor substrate 1, and , And a gate electrode GN formed thereon.

A p-channel type MISFET QP is formed in this logic circuit region. The p-channel type MISFET QP is formed on the n well 2a so as to be spaced apart from each other, and has a semiconductor region DP having an LDD (Lightly Doped Drain) structure, and a gate insulating film 4 formed on the semiconductor substrate 1. , And a gate electrode GP formed thereon.
n channel MISFET QN and p channel MISFET QP
Isolation is performed by a shallow trench burying type element isolation region 3a.
In the logic circuit area, logic logic circuits, memory cell sense amplifier circuits, and the like are arranged.

  In addition, a memory cell region mmry in which phase change memory cells are formed is located beside the logic circuit region. In this memory cell region, for example, an n-channel type memory cell selection MISFET QM is formed. The n-channel type memory cell selection MISFET QM is formed on the semiconductor substrate 1 and the semiconductor regions DN and DNC having an LDD (Lightly Doped Drain) structure formed on the p well 2 and spaced apart from each other. The gate insulating film 4 and the gate electrode GN formed thereon are provided. The semiconductor region DNC is shared by adjacent n-channel type memory cell selection MISFETs formed in the same element active region.

Such n-channel type MISFET QM, p-channel type MISFET QP, and n-channel type MISFET QN for memory cell selection are covered with interlayer insulating films 11 a and 11 b deposited on the semiconductor substrate 1. .
The interlayer insulating films 11a and 11b are made of, for example, a silicon oxide film, and are formed by, for example, a known plasma CVD method. The upper surface of the interlayer insulating film 11b is formed flat so that the memory region and the logic circuit region have substantially the same height.
Connection holes are formed in the interlayer insulating films 11a and 11b in the memory cell region mmry so that the upper surface of the semiconductor region DN of the memory cell selection MISFET QM is exposed.
In this connection hole, a barrier metal 12 made of, for example, a titanium film or a titanium nitride film and a conductive material 13 made of, for example, tungsten are embedded, and a high resistance conductive material 20 made of, for example, a titanium nitride film is further formed thereon. A lower contact electrode TP of the embedded memory cell is formed.
The lower contact electrode TP of the memory cell is electrically connected to the semiconductor region DN of the memory cell selection MISFET QM.
An interlayer insulating film 11c is deposited on the upper surface of the interlayer insulating film 11b. The interlayer insulating film 11c is made of, for example, silicon oxide.

A resistance element R serving as a memory element is formed in the interlayer insulating film 11c in the memory cell region.
The resistance element R is formed in a plate shape, for example, a film peeling prevention film 21 made of, for example, silicon nitride, a laser-crystallized phase change recording material film 27 coated on the surface thereof, and, for example, coated on the surface thereof. The memory cell upper plate electrode interface layer 23 made of tungsten, for example, and the memory cell upper plate electrode 24 made of tungsten, for example, are coated on the surface thereof. The phase change material film 27 constituting the resistance element R is made of, for example, chalcogenide Ge ₂ Sb ₂ Te ₅ or Ge ₃ Sb ₂ Te ₆ .
The lower portion of the resistance element R is electrically connected to the memory cell lower contact electrode TP, and is electrically connected to the semiconductor region DN of the n-channel type MISFET QM for memory cell selection through this.

In the interlayer insulating film 11c in the memory cell region mmry, a connection hole is formed so that the upper surface of the memory cell upper plate electrode 24 is exposed. A barrier metal 25 made of, for example, a titanium film or a titanium nitride film is buried in this connection hole, and further a metal film made of tungsten 26 is buried to form a memory cell upper electrode contact VM.
Bit line contact BC composed of barrier metal 25a and tungsten 26a is formed in semiconductor region DNC in memory cell region mmry. The bit line contact BC is electrically connected to the semiconductor region DNC shared by the memory selection n-channel type MISFETs QM1 and QM2.

A via electrode contact VL made of barrier metal 25a and tungsten 26a is formed in the semiconductor region DP in the logic circuit region lgc. The via electrode contact VL is electrically connected to the semiconductor region DP of the p-channel type MISFET QP.
In the semiconductor region DN in the logic circuit region lgc, a via electrode contact VL made of a barrier metal 25a and tungsten 26b is formed. The via electrode contact VL is electrically connected to the semiconductor region DN of the n-channel type MISFET.

The upper surface of the interlayer insulating film 11c is formed flat so that the heights of the memory region mmry and the logic region lgc are substantially the same.
An interlayer insulating film 11d is deposited on the upper surface of the interlayer insulating film 11c. This interlayer insulating film 11d is made of, for example, silicon oxide.
In the interlayer insulating film 11d, a bit line BL and a first layer wiring M1 are formed. The bit line is formed by depositing, for example, a barrier metal 28 made of a titanium film, a titanium nitride film, and tungsten 29 in order from the lower layer. The bit line BL is electrically connected to the bit line contact BC, and is further electrically connected to the semiconductor region DNC of the n-channel type MISFET QM for memory cell selection through the bit line contact BC.

  The first layer wiring M1 in the logic circuit region is formed by sequentially depositing, for example, a barrier metal 28 made of a titanium film, a titanium nitride film, and a tungsten film 29 from the lower layer. The first layer wiring M1 is electrically connected to the via electrode contact VL, and further through the via electrode contact VL, the semiconductor region DP of the p-channel type MISFET QP and the semiconductor region DN of the n-channel type MISFET QN. And are electrically connected.

Next, the main part layout of the memory cell region according to the first embodiment will be described with reference to FIGS.
First, as shown in FIG. 14, an active region (element active region or element forming region) L of an n-channel type MISFET having a gate electrode GN is formed on the p well. This gate electrode GN is used as a word line of the memory cell array.
A lower contact electrode TP of the memory cell is formed on the active region L of these n-channel type MISFETs.
A bit line contact BC is formed on the active region L of these n-channel type MISFETs. The bit line contact BC is formed to be convex with respect to the Y direction of the active region L of the n-channel MISFET.

Further, as shown in FIG. 15, the bit line BL is arranged so as to be connected to the upper portion of the bit line contact BC protruding in the Y direction of the active region L of the n-channel type MISFET. Yes.
Needless to say, the active regions L shown in FIGS. 14 and 15 are periodically arranged in the memory cell region.
Needless to say, the gate electrodes GN used as the word lines shown in FIGS. 14 and 15 are continuous in parallel in the memory cell region, that is, arranged in the X direction.
Needless to say, the bit lines shown in FIGS. 14 and 15 are continuous in parallel in the memory cell region, that is, arranged in the Y direction.

Hereinafter, the semiconductor integrated circuit device according to the present embodiment will be described in detail with reference to FIGS. Note that components having the same function are denoted by the same reference symbols throughout the drawings for describing the embodiments, and the repetitive description thereof is omitted.
First, a MISFET is formed using a known method. The semiconductor substrate 1 is made of, for example, a p-type silicon single crystal. In the semiconductor substrate 1 in the logic circuit region lgc and the memory cell region mmry, a p-well 2 is formed using a known method. An n well 2a is formed in the semiconductor substrate 1 in the logic circuit region lgc using a known method.
In such an upper layer portion of the semiconductor substrate 1, shallow trench buried type element isolation regions 3, 3 a, 3 b are formed using a known method. A region partitioned by this element isolation region (insulating films 3, 3a, 3b) is a so-called active region, and an element or the like is formed in a part of this region. The gate insulating film 4 on the semiconductor substrate 1 is made of, for example, silicon oxynitride, and the thickness thereof is set to about 1.5 to 10 nm, for example.

Next, an n-type polycrystalline silicon film 5 and a p-type polycrystalline silicon film 5a are formed using a known method. Next, the LDD active region 9 of the n-channel MISFET and the LDD active region 9a of the p-channel MISFET are formed using a known method. Next, sidewall spacers 7 made of, for example, a silicon oxide film, for example, sidewall spacers 8 made of, for example, a silicon nitride film, are formed using a known method. Next, an n-channel MISFET active region 10, a p-channel MISFET active region 10a, an n-type polycrystalline salicide film 6, and a p-type polycrystalline salicide film 6a are formed using a known method. Next, interlayer insulating films 11a and 11b are formed using a known method.
Thus, the salicide gate electrode structures GN and GP of the MISFET, the diffusion layer regions DN, DNC, DP, the side wall spacers 7 and 8, and the interlayer insulating films 11a and 11b are formed using a known method. The upper surface of the interlayer insulating film 11b is formed flat so that the heights of the memory region and the logic circuit region are substantially the same as shown in FIG.

Next, a photoresist for forming a connection hole in the memory cell region is formed on the interlayer insulating film 11b, and this is used as an etching mask for the semiconductor region QN of the n-type MISFET QM for memory cell selection on the interlayer insulating films 11a and 11b. A connection hole is drilled so that the upper surface is exposed (see FIG. 3).
Next, after removing the photoresist pattern, a barrier metal 12 made of, for example, a titanium film and a titanium nitride film is sequentially deposited on the semiconductor region DN from the lower layer by a sputtering method or the like. On the deposited film, for example, tungsten 13 is stacked by a CVD method or the like to fill the connection hole. By using a known CMP method, the upper portion of the interlayer film 11b is exposed.
Next, the tungsten 13 buried in the contact hole is etched back, for example, by 20 nm. Next, a high resistance metal 20 made of, for example, a titanium film and a titanium nitride film is sequentially deposited from the lower layer by sputtering or the like to fill the contact holes. When this is completely separated using a known CMP method, the memory cell lower contact electrode TP is completely separated as shown in FIG.

  In the present embodiment, the high-resistance metal 20 is used to fill the memory cell lower contact electrode hole. However, a metal having good CMP flatness such that the upper surface of the memory cell lower contact electrode is flat may be used. Good. For example, Mo (molybdenum) having a small crystal grain system can be used. A metal having good CMP flatness has an effect of suppressing local phase change due to electric field concentration occurring in the uneven portion of the contact metal. As a result, the uniformity of the electrical characteristics of the memory cell element, the reliability of the number of rewrites, and the high temperature resistant operation characteristics are improved.

A thin insulating film may be used on the upper surface of the memory cell lower contact electrode TP. For example, silicon oxide, silicon nitride, germanium oxide, or aluminum oxide can be used.
Also, tungsten oxide or tungsten nitride may be formed by oxidizing or nitriding, for example, tungsten 13 so that the upper surface of the memory cell lower contact electrode TP has a high resistance.
Next, when a phase change material made of silicon nitride, for example, is peeled off, a film 21 is deposited as shown in FIG.
Next, when the phase change material 22 is deposited, the result is as shown in FIG. The film thickness of the phase change material was 100 nm.
Next, when a metal film 23 made of tungsten, for example, is sequentially deposited, the result is as shown in FIG.
Next, when, for example, laser light is irradiated from the upper surface of the metal film 23 to form the phase-change material 27 crystallized by annealing, the result is as shown in FIG.

FIG. 18 is a schematic view of the laser crystallization apparatus used.
The laser head 36 is collected by a high-power semiconductor laser 47 that is a light source, a collimator lens 35B, a PBS 35A, an objective lens 35 that condenses the laser light, an actuator 49 that moves the objective lens 35 in the optical axis direction 5C, and an objective lens 45. The focus detector 40 detects the position of the illuminated focus point. The wafer tray 39 on which the disc-shaped silicon wafer 38 is mounted is dug out with a diameter slightly larger than the diameter of the silicon wafer 38, and is disposed so as to be orthogonal to the optical axis 5C of the laser light passing through the objective lens 35. The wafer tray 39 can be freely moved two-dimensionally in the X-axis direction 46 and the Y-axis direction 45 while maintaining the right angle.

The laser drive circuit 41 can emit pulses, and can perform laser pulse drive with a frequency of 1 Hz to 10 MHz and a pulse width of 100 ns to 1 s. DC drive is also possible. Furthermore, the top output and bottom output of the laser pulse light can be arbitrarily set.
The focus control circuit 42 has a feedback control function that drives the actuator 49 based on the focus deviation signal detected by the focus detector 40 to correct the focus deviation.
The XY table control circuit 44 can drive the wafer tray 39 on a two-dimensional plane in the X-axis direction 46 and the Y-axis direction 45 so that arbitrary speed and arbitrary positioning can be performed in the X and Y directions. It has become.
The microprocessor (MPU) 43 is connected to main parts of a laser drive circuit 41, an XY table control circuit 44, a signal processing circuit 48, a focus control circuit 42, and a head drive circuit (not shown). It is designed to perform pre-programmed operations and can control each main part at once.
Further, when high laser power density is not required, parallel light may be used without focusing by an objective lens or the like. The light source is not limited to a semiconductor laser, but may be a solid laser such as a YAG laser or a CO ₂ laser, or a gas laser. The flash light from the xenon flash lamp may be condensed and irradiated by a reflecting mirror or the like.

A scanning method of the laser beam on the wafer will be described with reference to FIG. FIG. 19A illustrates a method in which the stage is linearly scanned at a constant speed only in the X direction while continuously reciprocating the laser beam in the direction perpendicular to the longitudinal direction of the spot, that is, the front and back directions in FIG. It is a figure to do. At this time, the trajectory drawn by the midpoint of the beam always intersects at the same angle. The beam spot turns as soon as it reaches the edge of the region to be crystallized on the wafer, but the inertia is large when driving the entire optical head, so the trajectory is not a shape where the straight line is completely folded at an acute angle. Rounded. The speed and turn-back position are determined so that the beam spot (range up to 1 / e ² of the maximum power) always passes through any point in the region to be crystallized on the wafer at least once. FIG. 19B shows a locus drawn by the midpoint of the beam when the beam spot is scanned on the wafer by alternately moving the optical head and the X stage. In the figure of the silicon wafer 50 being crystallized as seen from the laser head 36 side, the horizontal direction is the X axis and the vertical direction is the Y axis. This figure is for an arbitrary time during crystallization. The laser spots 59A and 69A are moving in the Y direction 59 and 69. The left half of the silicon wafer 50 is crystallized 56 and the right half is uncrystallized. Part 57. Initially, the laser spots 59, 69 are at positions 52,62. Laser light is emitted at a predetermined pulse frequency and output, and focus control is performed. The laser spot is scanned while crystallizing the silicon wafer 50 in the 53 direction by moving the laser head in the Y direction. When the laser spot reaches the edge of the silicon wafer 50, the movement in the Y direction is stopped, and the silicon wafer 50 is moved in the X direction 54 by a distance shorter than the laser spot width 58. After that, the laser head is moved 55 in the Y direction. The entire surface of the silicon wafer 50 can be crystallized by repeating the above operation and scanning the laser spot from the left surface of the silicon wafer so as not to generate an uncrystallized gap. A silicon wafer may be moved instead of the laser head. In this example, the laser spot area is 10 ⁻⁶ cm ² or more and 10 ⁻³ cm ² or less, and the pulse width (passage time in the range of 1 / e ² of the maximum power of the spot) is from 100 ns to 1 s. I was able to confirm.

  In the linear scanning laser crystallization apparatus described with reference to FIG. 16, the laser head 36 is moved in the Y direction and the silicon wafer 38 mounted on the wafer tray 39 is moved in the X direction. A laser head XY plane moving mechanism (not shown) for moving the head 39 in both the X-axis direction and the Y-axis direction is provided, and the entire surface of the silicon wafer 50 is crystallized in the same manner as the laser spot scanning described with reference to FIG. Also good. In addition, the laser head 36 is movable only in the X-axis direction and the silicon wafer 38 mounted on the silicon tray 39 is movable only in the Y-axis direction, or the laser head 36 is movable only in the Y-axis direction and mounted on the tray 39. It is also possible to crystallize the entire surface of the silicon wafer in the same manner as the laser spot scanning described with reference to FIG.

  In the example of FIG. 16, the laser head 36 is arranged above the silicon wafer 38, that is, when the vertical direction is used as a reference, the laser head 36) is disposed at a position higher than the silicon wafer 38. 36 may be disposed below the silicon wafer 38. Further, the gap between the silicon wafer 38 and the laser head 36 may be partitioned by a transparent plate. Further, the silicon wafer 38 and the wafer tray 39 may be integrated, or the laser head 36), the silicon wafer 38) and the wafer tray 39 may be installed in a vacuum film forming apparatus, or a container in which a specific gas is sealed. It may be installed inside. The laser head may be installed outside the vacuum of the vacuum film forming apparatus, and the laser beam may be introduced into the vacuum.

When observed with a transmission electron microscope by laser crystallization as described above, a vertically long crystal having a width smaller than 100 nm and a width of about 20 to 50 nm was observed. In this case, since the width of the lower electrode is smaller than about 80 nm, as described in detail later, an excellent device was obtained without variation in element characteristics due to the relative positional relationship between the crystal and the lower electrode.
Next, when the metal film 24 made of tungsten, for example, is sequentially deposited, the result is as shown in FIG.
Next, the phase change material peeling prevention film 21, the laser-crystallized phase change material 27, tungsten 23, and tungsten 24 are processed as a resistance element R, as shown in FIG.
Next, when the interlayer film 11c is deposited, the result is as shown in FIG.
Next, by lithography and dry etching processes, the interlayer film 11c is drilled in the memory cell region mmry to form connection holes, and the interlayer films 11a, 11b, and 11c are drilled in the memory cell region mmry to form logic holes. In the circuit region lgc, the interlayer films 11a, 11b, and 11c are drilled to form connection holes, and the barrier metal 25 and tungsten 26 are deposited in this order. This connection hole is buried, and etching back is performed until the upper surface of the interlayer film 11c is exposed and the upper surface of the tungsten 26 and the interlayer film 11c in the hole are at the same height, and the upper electrode contact VM of the memory cell region and the memory cell region The bit line contact BC and the via electrode contact VL in the logic circuit region are completely separated as shown in FIG.
Next, after depositing an insulating film 11c made of, for example, silicon oxide, a first layer wiring of a logic circuit and a photoresist for forming a bit line are formed on the interlayer insulating film 11c, and the interlayer insulating film is formed using this as an etching mask. A first layer wiring groove and a bit line groove of the logic circuit are formed so as to expose the upper surface of 11b. Next, a barrier metal film 29 made of, for example, a titanium film and a titanium nitride film is sequentially deposited from the lower layer by a sputtering method or the like, and a conductor film is formed thereon by stacking, for example, a tungsten film 28 by a CVD method or the like. The CMP method is used to etch back until the upper surface of the interlayer film 11c is exposed and the upper surface of the bit line BL and the first layer wiring M1 in the trench has the same height, and the bit line BL and the first layer wiring M1 are When completely separated, FIG. 13 is obtained.
A plurality of wiring layers are formed on the wiring layers of the wiring M1 and the bit line BL by a known method, but illustration of them is omitted.

In addition, the semiconductor memory device is completed after hydrogen annealing at about 400 ° C. to 450 ° C. is performed using a known method.
Regarding the above-mentioned memory, the relationship between the material and various conditions for manufacturing and the memory characteristics will be described below.
When the ratio between the maximum width of the contact portion of the electrode with the smaller maximum width of the contact portion of the contact region with the phase change film and the average width when cut parallel to the film surface of the crystal grain is changed, The result was as follows. Note that the average width in the cross section parallel to the film surface of the crystal grain is 10 cross-sectional TEM photographs showing an example in FIG. It was defined as the average value at the center in the film thickness direction of the width when a total of 20 were selected.

  When a reset pulse is first applied, the phase change film near the electrode with the smallest contact width is melted by current heating, and then rapidly cooled to become amorphous after being heated. Crystals remain. In addition, the atomic arrangement of the amorphous region is not completely calculated because the melting time is very short, and some past history remains. Therefore, when the set pulse is next applied, the current path is affected by the crystal grain boundary, and the shape of the crystal grain during laser crystallization is affected (see Table 1).

  That is, the phase change memory has a reversible phase change between the crystalline phase and the amorphous phase formed on the base, the first electrode formed on the base, and the first electrode. It is necessary to have a phase change film capable of recording information by waking up and a second electrode formed on the phase change film. Of the electrodes on both sides of the phase change film, the average width when cut parallel to the film surface of the crystal grains needs to be smaller than the electrode having the smaller maximum width of the contact region with the phase change film.

  The average width in the cross section parallel to the film surface of the crystal grains of the phase change film (film thickness 100 nm) judged from the transmission electron micrograph of the cross section as shown in FIG. 20 (the average of any 20 adjacent crystal grains) Was smaller than the average width in the direction perpendicular to the film surface (film thickness direction). The average width in a cross section parallel to the film surface of the crystal grains is about 20 nm. Crystal grains can be columnar even with normal heat treatment, but each column is thicker than in the case of laser crystallization. In laser light irradiation, the extinction coefficient of the phase change film is large, so absorption occurs mainly near the light incident side surface of the film, and the temperature inside the film rises sequentially due to heat conduction, so crystal growth is perpendicular to the film surface. It is thought that it is easy to happen. The crystal grains do not need to reach both interfaces of the film. For example, in the case of FIG. 20, the crystal grains grow from the interface on the light incident side, and the growth seems to stop immediately before reaching the opposite interface. is there. In the part where the growth has stopped, the tip of the crystal grain appears to be rounded or polygonal. FIG. 21 shows an example in which the laser power is lowered to crystallize from the light incident side to near half the film thickness.

  An example of the relationship between the resistance value and the set pulse width is shown in FIG. This example is a case of a phase change film to which a large amount of nitrogen having a low crystallization rate is added. When the width of the crystal grain is difficult to change and the height changes, the average width in the cross section parallel to the film surface of the crystal grain of the phase change film judged from the transmission electron micrograph of the cross section and the direction perpendicular to the film surface (film When the ratio to the average width (thickness direction) was changed, the shortest set pulse width changed as follows because crystals that were not melted at the time of resetting were easier to crystallize due to the action of current when they were longer in the film thickness direction. .

  The ratio of the average width in the cross section parallel to the film surface of the crystal grains of the phase change film to the average width in the direction perpendicular to the film surface (film thickness direction) and the shortest set pulse width are shown in the following table (see Table 2).

That is, in order to reduce the characteristic variation between elements to a practical level, the above ratio is preferably smaller than the average width in the cross section parallel to the film surface of the crystal grain than 1: 2. It is more preferable that the ratio is 1: 3 or more.
The composition of the phase change film is also important because it has a predetermined crystal grain shape even after passing through the memory fabrication process. For example, in a well-known film of Ge ₂ Sb ₂ Te ₅ composition, after laser crystallization, the crystal grains are elongated in the film thickness direction and the cross-sectional aspect ratio is 5: 1 or more. After passing, it seemed that several crystal grains were fused.
Table 3 below shows the relationship between the composition (atomic ratio) and the size of the crystal grains after the 400 ° C. process (in the direction parallel to the film surface).

  The same applies when Zn is replaced by Cd, which is a homologous element, and Ag is replaced by another transition metal element such as Co. With regard to the addition amount, an effect of reducing the crystal grains is seen in the range of 1 atomic% to 30 atomic%, but a more preferable range is from 2 atomic% to 25 atomic%. In a film containing Zn or Cd whose crystal grains tend to be small, there are many crystal grains that have formed crystal nuclei at the center of the film and have not reached both interfaces.

  To summarize the above results, the phase change film contains at least one element of the group consisting of Te, Ge, Sb, and Bi, and in addition, Zn, Cd, In, N, O , Consisting of a material composed of at least three elements containing at least one of the transition metal elements in an amount of not less than 1 atom% and not more than 30 atom%, forms crystal grains of a predetermined shape, and undergoes a process at 400 ° C. Is also preferred because it is almost preserved.

FIG. 17 shows an example of the measurement result of the resistance value at the time of rewriting many times when laser crystallization is not performed. Note that both set and reset were performed at 5V. The figure shows the change after 10 rewrites. From 1 to 10 times, the set resistance decreased from about 5 × 10 ⁵ Ω to about 1 digit while fluctuating. It is necessary to raise the temperature sufficiently at the time of laser heating so as to reduce dangling bonds and voids as much as possible, and to reduce the characteristic change after the beginning and after rewriting. Although it is a feature of laser irradiation that the time during which the temperature is high during and after irradiation can be shortened to prevent adverse effects of temperature rise such as film deformation and oxidation, it is still difficult to completely prevent oxidation. Therefore, it is more preferable to perform laser irradiation after forming a protective film that is unlikely to be an obstacle to laser heating. Since the protective film becomes an interface layer after completion of the phase change memory, it should not completely block electrical conduction (see Table 4).

Similar results can be obtained by replacing W with a material such as W ₈₀ Ti ₂₀ that has W as the main component (greater than 50 atomic%).
Therefore, it is particularly preferable that the film has the same composition as that of the metal of the electrode formed thereon.
The thickness of this layer is preferably 2 nm or more and 20 nm or less in order to obtain an effect and to prevent insufficient light absorption.

When a thin film is not formed on the phase change film or only a thin film is formed, it is heated to high temperature by laser irradiation to form a crystal state free from dangling bonds and voids. Compared to the method of rewriting the element many times, not only does it take a long time, but also distortion due to volume change is easily relieved, so that a defective element is hardly generated.
In an experiment corresponding to rewriting 100 times for all elements during the aging process, the rewrite resistance value reached a stable value for many elements. However, because the upper structure is formed with distortion and film defects due to large crystal grains, the film structure is relaxed as a whole and only the energized part is heated without moving. Many elements were produced.
That is, information is generated by causing a reversible phase change between a crystal phase and an amorphous phase formed on the base, the first electrode formed on the base, and the first electrode. It is preferable to include a phase change film for recording the film, an interface layer formed on the phase change film, and a second electrode formed on the interface layer.

When the shape of the irradiated light spot and the transit time of the light spot were changed, the following results were obtained. The spot area was an experiment including two types of light spots including defocus. As a small spot, the effect was obtained up to 10 ⁻⁶ cm ² at 100 μm × 1 micron of a laser of 2 W output, and as a large spot to a spot of about 10 ⁻³ cm ² of 3.5 mm × 30 μm of a laser of 60 W output. However, particularly in the range of 2 × 10 ⁻⁶ cm ² or more and 10 ⁻⁴ cm ² or less, the resistance value was stabilized from the first rewriting irrespective of the conditions of the aging treatment before shipment.
The effect was obtained if the irradiation time (the time until the peak intensity of the light spot reaches 1 / e ² through one point on the disk) was 0.1 μs or more and the irradiation power was optimal, but if it was 1 s or more, the effect was obtained. It was difficult to prevent partial peeling of the interface due to heat. Good characteristics with particularly good reproducibility were obtained at 1 μs or more and 1 ms or less.
In the case of a phase change transistor, laser irradiation to a phase change film having a memory function can be performed in the same manner, and the same effect can be obtained.

To summarize the above results:
A step of forming a first electrode on a substrate; and a phase change recording film for recording information by causing a reversible phase change between a crystalline phase and an amorphous phase on the first electrode. Crystallizing the phase change recording film by laser light irradiation under conditions of a spot area of 10 ⁻⁶ cm ^{2 to} 10 ⁻³ cm ² and an irradiation time of 0.1 μs to 1 s and the phase change. Forming a second electrode on the recording film, and a phase change memory having a minute crystal grain in the phase change film formed thereby, It turns out that it is preferable.

1 is a main-portion cross-sectional view of a semiconductor integrated circuit device that is Embodiment 1 of the present invention; FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 3 is a fragmentary cross-sectional view of the substrate during a manufacturing step of the semiconductor integrated circuit device shown in FIG. 1. FIG. 2 is a main part layout diagram of the semiconductor integrated circuit device shown in FIG. 1. FIG. 2 is a main part layout diagram of the semiconductor integrated circuit device shown in FIG. 1. This is a basic structure of a memory cell of a phase change memory. It is an example of the many-time rewriting characteristic of a phase change memory. It is the schematic of one example of a laser crystallization apparatus. (a) And (b) is a figure explaining the scanning of a laser beam. It is a figure (photograph) which shows the crystal grain formed in the phase change film in one Example of this invention. It is a figure (photograph) which shows the crystal grain formed in the middle of the film thickness direction in the phase change film in one Example of this invention. It is an example of the relationship between the set pulse width and resistance value of a phase change memory.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Semiconductor substrate, 2 ... p well, 2a ... n well, 3, 3a, 3b ... Element isolation groove, 4 ... Gate insulating film, 5 ... n-type polycrystalline silicon film, 5a ... p-type polycrystalline silicon film, 6 ... n-type polycrystalline salicide film, 6a ... p-type polycrystalline salicide film, 7 ... sidewall spacer (silicon oxide film), 8 ... sidewall spacer (silicon nitride film), 9 ... LDD active region of n-channel MISFET, 9a... LDD active region of p channel MISFET, 10... Active region of n channel MISFET, 10a... Active region of p channel MISFET, 11a, 11b, 11c, 11d. Barrier metal, 13 ... tungsten, 20 ... high resistance conductive material, 21 ... phase change material peeling prevention film (insulating film), 22 ... phase change material layer, 27 ... annealing Crystallized and phase change material layer, 23,24,26,28 ... tungsten film (metal film), 25, 29 ... metal barrier,
mmry ... memory cell formation region,
lgc: logic circuit formation region,
DN: active region of n-channel MISFET,
DNP: active region of n-channel MISFET,
DP: active region of p-channel MISFET,
GM: n-channel MISFET gate electrode for memory cell selection,
GN: gate electrode of n-channel MISFET,
GP: gate electrode of p-channel type MISFET,
QM: n-channel type MISFET for memory cell selection,
QN: n-channel type MISFET,
QP ... p-channel MISFET,
TP ... Memory cell lower contact electrode,
BC: Bit line contact electrode,
BL ... bit line,
R: resistance element,
VM: Memory cell area via,
VL: Logic circuit area via,
M1 ... first layer wiring,
L: Element active region of MISFET,
31 ... Phase change material, 35 ... Objective lens for condensing laser light, 35A ... PBS, 35B ... Collimator lens, 35C ... Optical axis direction, 36 ... Laser head, 40 ... Focus detector, 41 ... Laser drive circuit, 42 ... focus control circuit, 43 ... microprocessor, 44 ... XY table control circuit, 45 ... Y-axis direction, 46 ... X-axis direction, 47 ... high-power semiconductor laser, 48 ... signal processing circuit, 49 ... actuator, 50 ... Silicon wafer, 56 ... crystallized part, 57 ... uncrystallized part, 58 ... laser spot width, 59 ... laser spot, 59A ... laser spot.

Claims (16)

A substrate;
A first electrode formed on the substrate;
A phase change film formed on the first electrode and capable of recording information by causing a reversible phase change between a crystalline phase and an amorphous phase;
A second electrode formed on the phase change film,
The phase change film is a maximum dimension of a portion of the electrode formed in direct or indirect contact with the main surface of the phase change film, or a surface facing directly or indirectly in contact with the main surface. When the electrode is formed in a direction along the surface of the substrate at the center in the film thickness direction in a cross section perpendicular to the surface of the substrate, whichever is smaller than the maximum dimension of the portion of the electrode in contact with the phase change film, whichever is smaller A semiconductor memory, wherein an average width of crystal grains of the phase change film is small.   The average width of the crystal grains when cut in a direction along the surface of the substrate is smaller than the average width of the crystal grains when cut in the film thickness direction of the phase change film. The semiconductor memory described in 1. The phase change film contains Te and an element selected from at least one of a group of Ge, Sb, or Bi;
In addition, the element selected from at least one of Zn, Cd, In, N, O, and a transition metal element group is contained in an amount of 1 atomic% to 30 atomic%. The semiconductor memory as described. A substrate;
A first electrode formed on the substrate;
A phase change film formed on the first electrode for recording information by causing a reversible phase change between a crystalline phase and an amorphous phase;
An interface layer formed on the phase change film;
A second electrode formed on the interface layer,
The phase change film has a maximum dimension of a portion directly or indirectly contacting the phase change film of the electrode formed on the main surface of the phase change film or a minimum dimension of the electrode formed on the surface facing the main surface. A semiconductor memory, wherein an average width of crystal grains of the phase change film when cut in a direction along the surface of the base is smaller than a minimum dimension of any one of the smaller electrodes.   5. The average width of the crystal grains when cut in a direction along the surface of the substrate is smaller than the average width of the crystal grains when cut in the film thickness direction of the phase change film. The semiconductor memory described in 1. The phase change film contains Te and an element selected from at least one of a group of Ge, Sb, or Bi;
In addition, the element selected from the group consisting of Zn, Cd, In, N, O, and transition metal elements is contained in an amount of 1 atomic% to 30 atomic%. The semiconductor memory as described. Preparing a substrate;
Forming a transistor on the substrate;
Forming an interlayer film on the region including the transistor;
Providing a conductive layer in the interlayer film so as to be connected to one of the terminals of the transistor;
Forming a first electrode on the interlayer film so as to be connected to the conductive layer;
Forming a phase change film capable of recording information by causing a reversible phase change between a crystalline phase and an amorphous phase on the first electrode;
Irradiating light from the upper surface of the phase change film;
Forming a second electrode on the phase change film;
A method for manufacturing a semiconductor memory, comprising: Forming an interface layer after forming the phase change film;
The method of manufacturing a semiconductor memory according to claim 7, further comprising a step of irradiating light from an upper surface of the interface layer.   9. The method of manufacturing a semiconductor memory according to claim 8, wherein the interface layer is made of any material of oxide, nitride, or metal.   8. The method of manufacturing a semiconductor memory according to claim 7, wherein a laser or a flash lamp is used as the light source in the light irradiation.   8. The method of manufacturing a semiconductor memory according to claim 7, wherein the interface layer is made of any material of oxide, nitride, or metal. The light irradiation step is characterized by crystallization by laser light irradiation using conditions of a spot area of 10 ⁻⁶ cm ² or more and 10 ⁻³ cm ² or less and an irradiation time of 0.1 μs or more and 1 s or less. 8. A method of manufacturing a semiconductor memory according to claim 7.   The conductive layer is formed by embedding a metal material in a through-hole provided through the interlayer film, and the phase change film is formed on the interlayer film so as to cover the conductive layer region. The method of manufacturing a semiconductor memory according to claim 7. Preparing a substrate;
Forming an interlayer film on the substrate;
Providing a conductive layer in the interlayer film;
Forming a first electrode on the interlayer film so as to be connected to the conductive layer;
Forming a phase change film capable of recording information by causing a reversible phase change between a crystalline phase and an amorphous phase on the first electrode;
Irradiating light from the upper surface of the phase change film;
Forming a second electrode on the phase change film;
A method for manufacturing a semiconductor memory, comprising:   15. The method of manufacturing a semiconductor memory according to claim 14, wherein a laser or a flash lamp is used as the light source in the light irradiation. The light irradiation step is characterized by crystallization by laser light irradiation using conditions of a spot area of 10 ⁻⁶ cm ² or more and 10 ⁻³ cm ² or less and an irradiation time of 0.1 μs or more and 1 s or less. The method of manufacturing a semiconductor memory according to claim 14.

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