This Nonprovisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2004-004949 filed in Japan on Jan. 13, 2004, the entire contents of which are hereby incorporated by reference.
1. Field of the Invention
The present invention relates to a nonvolatile semiconductor memory device and, more specifically, to a manufacturing method of a nonvolatile semiconductor memory device including a variable resistive element having a variable resistor made of a perovskite-type metal oxide film.
2. Description of the Related Art
In recent years, a variety of device structures such as an FeRAM (Ferroelectric RAM), an MRAM (Magnetic RAM) and an OUM (Ovonic Unified Memory) have been proposed as a next generation nonvolatile random access memory (NVRAM) that makes a rapid operation possible substituting a flash memory, and there has been a fierce competition for the development of such devices from the standpoint of increase in performance, increase in reliability, cost reduction and process matching. However, these memory devices at the present stage have their merits and demerits, and there is a long way to go before the realization of an ideal “universal memory” which has the respective merits of an SRAM, a DRAM and a flash memory.
The FeRAM, for example, which has already been put into practice, utilizes a spontaneous polarization inversion phenomenon of oxide ferroelectrics and is characterized by a low consumed power and a high speed operation; however, it is inferior due to high cost and destructive readout. A ferromagnetic tunnel effect element that utilizes giant magnetoresistance (GMR) used in the MRAM has a structure in that two ferromagnetic layers made of Fe, Co, Ni or the like is placed between extremely thin insulating layers (tunnel barrier layers) such as Al2O3. Herein, an amount of tunnel current flowing via the insulating layers can be controlled by changing the orientation of magnetization (spin) of the ferromagnetic layers, thus exhibiting a memory effect. This element has a large problem of high consumed power for magnetization inversion at the time of programming and of a difficulty in miniaturization. In addition, the OUM based on thermal phase transformation of a chalcogenite material is advantageous in low cost and process matching; however, it has a problem in miniaturization and in a high speed operation due to its thermal operation.
In addition to these existing technologies, a resistive random access memory (RRAM) device, that utilizes an electrical pulse induced resistance (EPIR) effect which is a new phenomenon in a colossal magnetoresistance (CMR) material, has been disclosed (see U.S. Pat. No. 6,204,139) by Shangquing Liu, Alex Ignatiev et al. of Houston University in the United States. The EPIR effect in a CMR material represented by a Mn-based oxide material having a perovskite-type structure is epoch-making where a change in resistance by several digits occurs at room temperature. The RRAM that utilizes this phenomenon has features in a low consumed power, a simple structure appropriate for miniaturization, easiness in a high integration and a wide dynamic range of a change in the resistance, and has excellent properties where a multiple value memory, which stores information of three or more values in a single memory element, is made possible. The memory element has an extremely simple basic structure where a lower electrode thin film, a CMR thin film and an upper electrode thin film are layered in sequence in the direction perpendicular to a substrate. According to the operation, the polarity, the voltage and the pulse width (widely ranging from several tens of ns to several μs) of the electrical pulse that is applied between the upper and the lower electrodes are controlled, so that the resistance of the CMR thin film that is placed between the upper and lower electrodes is changed. The resistance value that has been changed due to such a pulse application is maintained for a long period of time after the pulse application, and the performance of a nonvolatile memory element can be obtained by, for example, making the low resistance condition correspond to “0” and making the high resistance condition correspond to “1”.
As the CMR material of an EPIR element, Pr1-xCaxMnO3 (PCMO), La1-xCaxMnO3, La1-xSrxMnO3, Gd0.7Ca0.3BaCo2O5+5 or the like, which have a perovskite structure, where the base is a network of oxygen octagons having a 3d transition metal element at its center, are typically used, and there has been reported that PCMO having the composition that is dose to x=0.3 has the widest range of a change in the resistance value. As the electrode material, metal-based materials such as Pt, Ir, Ru, Ph, Ag, Au, Al and Ta and oxide- or nitride-based compounds such as YBa2Cu3O7-x, RuO2, IrO2, SrRuO3, TaSiN, TiN, TiSiN and MoN which have a conductivity higher than the CMR material are used and noble metal-based materials which are superior in mass production and form an excellent interface condition with the CMR layer, causing no problems with the electrical connection and which include metals in the platinum group such as Pt (lattice constant a=0.3923 nm), Ir (a=0.3839 nm), Rh (a=0.3803 nm) and Pd (a=0.389 nm) as well as Au (a=0.4079 nm) are appropriate.
In the case where nonvolatile memory elements are formed simultaneously with the formation of transistors at the time when the nonvolatile memory elements are fabricated in a semiconductor integrated circuit according to the prior art, heat treatment is carried out to the nonvolatile memory elements at a high temperature by diffusion annealing used for formation of transistors, so that the film quality of the perovskite-type metal oxide for the performance of the nonvolatile memory elements is changed. Accordingly, it is desirable to form the nonvolatile memory elements in the wiring process after formation of the transistors in order to integrate the nonvolatile semiconductor memory elements into the semiconductor integrated circuit. In addition, the nonvolatile memory elements can be fabricated in a layered structure by fabricating the nonvolatile memory elements in the wiring process, so that high integration becomes possible and specification change and design change of the semiconductor integrated circuit become easy.
In the wiring process of manufacturing a semiconductor integrated circuit, with Al wires, the melting point is too low, 660° C., and with Cu wires of which the specific resistance is lower than that of Al wires, Cu wires are easily to diffuse into an insulating layer at a high temperature so that the heat treatment can not be carried out after formation of the wires. As a result, it is necessary to form nonvolatile memory elements by using a low temperature process in order to add a process for fabricating nonvolatile memory elements after formation of the wires in manufacturing a semiconductor integrated circuit. A method for forming a perovskite-type metal oxide film using a low temperature process is not clarified according to the prior art disclosed in U.S. Pat. No. 6,204,139 by Houston University in the United States.
The present invention has been made in view of the above problems, and it is therefore an object to provide a method for forming a nonvolatile memory element in a wiring process in which the high integration by a layered structure and design change are easy at the time a nonvolatile memory element having a variable resistor made of a perovskite-type metal oxide film is fabricated in a semiconductor integrated circuit, and a manufacturing method of a nonvolatile memory element that can be formed in a low temperature process not causing thermal damage in a wiring process.
As for the relationship between the film forming temperature and the resistivity of a perovskite-type metal oxide film, in an example of a PCMO film as shown in
Accordingly, in a nonvolatile semiconductor memory device including a variable resistive element (see
More preferably, the manufacturing method is characterized in that the variable resistor is a praseodymium calcium manganese oxide represented by a general formula, Pr1-xCaxMnO3, of which the film has been formed at a film forming temperature between 350° C. and 500° C. A Pr1-xCaxMnO3 (PCMO) film that has been formed at a film forming temperature between 350° C. and 500° C. has properties of great resistance change held by a PCMO film and, also, has the working effects described above.
More preferably, the manufacturing method is characterized in that the variable resistor is formed above the metal wire layer which is the lowermost layer. In the case where a memory cell is assumed to be formed of a variable resistive element and an active element such as a transistor, the variable resistive element and the transistor can be placed on top of each other, achieving the miniaturization of the memory cell. In addition, the variable resistor is formed in a low temperature process; therefore; the metal wire placed at the lower layer can be prevented from being thermally damaged.
A manufacturing method of a nonvolatile semiconductor memory device according to a first aspect of the present invention is a manufacturing method of a nonvolatile semiconductor memory device including a variable resistive element having a variable resistor made of a perovskite-type metal oxide film, and the variable resistor is formed at a temperature lower than the melting point of the metal wire layer that has been formed before formation of the variable resistor.
According to the manufacturing method of a nonvolatile semiconductor memory device with the first aspect, first, the variable resistor made of a perovskite-type metal oxide film is formed at a temperature lower than the melting point of the metal wire material; therefore, the metal wire can be prevented from being thermally damaged excessively, so that a high quality nonvolatile semiconductor memory device can be obtained. Secondly, the resistivity of the perovskite-type metal oxide film changes depending on the film forming temperature; therefore, initial resistance can be set in accordance with the properties required for the variable resistive element without modifying the geometric dimensions, such as the film thickness of the variable resistor by adjusting the film forming temperature.
Furthermore, the manufacturing method of a nonvolatile semiconductor memory device according to a second aspect of the present invention is a manufacturing method of a nonvolatile semiconductor memory device including a variable resistive element having a variable resistor made of a perovskite-type metal oxide film, wherein the variable resistor made of praseodymium calcium manganese oxide represented by a general formula, Pr1-xCaxMnO3 is formed at a film forming temperature between 350° C. and 500° C.
According to the manufacturing method of a nonvolatile semiconductor memory device with the second aspect, first, the resistivity of the Pr1-xCaxMnO3 (PCMO) film changes depending on the film forming temperature between 350° C. and 500° C.; therefore, the initial resistance can be set in accordance with the properties required for the variable resistive element without modifying the geometric dimensions, such as the film thickness of the variable resistor by adjusting the film forming temperature. Secondly, the variable resistor is formed of a PCMO film at a temperature lower than the melting point of the metal wire material; therefore, the metal wire can be prevented from being thermally damaged excessively, so that a high quality nonvolatile semiconductor memory device can be obtained.
Preferably, in the manufacturing method of a nonvolatile semiconductor memory device according to any of the first and second aspects of the present invention, according to a third aspect of the present invention, the variable resistive element is formed by layering a lower electrode, the variable resistor and an upper electrode in sequence and the variable resistor is formed of a film on the lower electrode by means of sputtering in the process forming the variable resistive element.
According to the manufacturing method of a nonvolatile semiconductor memory device with third aspect, the variable resistive element is formed in such a manner that the variable resistor is placed between the lower electrode and the upper electrode; therefore, a predetermined voltage can be applied between the lower electrode and the upper electrode, so that this voltage can be applied to the variable resistor, changing the resistance value thereof and thereby, the variable resistive element formed of the lower electrode, the variable resistor and the upper electrode can function as a nonvolatile memory element. In addition, a sputtering method where parameters for film growth can be set in a wide range is used for forming the variable resistor; therefore, the formation of a high quality film at a low temperature becomes possible.
More preferably, in the manufacturing method of a nonvolatile semiconductor memory device according to the third aspect of the present invention, according to a fourth aspect of the present invention, the lower electrode and the upper electrode are formed at a temperature below a temperature, at which the variable resistor is formed, in the process of forming the variable resistive element. As a result, the metal wire that has already been formed can be prevented from being thermally damaged at the temperature, at which the lower electrode and the upper electrode are formed, so that a high quality of nonvolatile semiconductor memory device can be obtained.
More preferably, in the manufacturing method of a nonvolatile semiconductor memory device according to any of the above aspects of the present invention, according to a fifth aspect of the present invention, the variable resistor is formed at a temperature which is higher than a maximum treatment temperature in a process after formation of the metal wire layer. As a result, the variable resistor film that has been once formed is not annealed at a temperature higher than the film forming temperature; therefore, the initial resistance value that is determined by the film forming temperature can be stably maintained, so that the initial resistance value of the variable resistor can easily be adjusted.
One embodiment of a nonvolatile semiconductor memory device according to the present invention (hereinafter, appropriately referred to as “inventive device”) is described below with reference to the drawings.
As for the perovskite-type metal oxide that is used as the variable resistor 8, a great number of examples such as Pr1-xCaxMnO3 (PCMO), Pr1-x(Ca,Sr)xMnO3, Nd0.5Sr0.5MnO3, La1-xCaxMnO3, La1-xSrxMnO3 and Gd0.7Ca0.3BaCo2O5+5 are known. Among these, Pr1-xCaxMnO3-based materials, which have a large distortion in the network of the transition metal-oxide bonding and where a charge order phase is easily formed due to the suppression of charge transfer resulting from the distortion, exhibit a greater EPIR effect and moreover, the composition which is in the proximity of the phase border that is close to x=0.3 where a fusion phenomenon of the charge order phase easily occurs due to an external disturbance is preferable as the material used for the variable resistor 8 of the present invention that exhibits the EPIR effect.
As for the lower electrode 7, single noble metals including metals in the platinum group represented by Pt, Pd, Rh and Ir which have a high level of lattice matching with a perovskite-type metal oxide and have a high conductivity and a high resistance to oxidation and alloys between such noble metals as well as a variety of alloys of which the bases are these metals are preferable.
On the other hand, the upper electrode 9 is not necessarily exposed to an oxygen atmosphere at a high temperature; therefore, it is not limited to the above noble metal elements but rather a variety of materials such as Al, Cu, Ni, Ti and Ta, as well as oxide conductors are applicable. Here, a barrier layer may appropriately be inserted between the lower electrode and the base substrate in order to prevent reaction and to improve adhesion. In the case where an electrical connection is secured between the substrate and the lower electrode when a silicone substrate is used, for example, a significant conversion to an alloy occurs between Pt and Si; therefore, insertion of Ti, TiN, Ti1-xAlxN, TaN, TiSiN, TaSiN or the like, which has a conductivity and a barrier function, is effective. In the case where the substrate is coated with a SiO2 layer, use of TiOx, IrO2 or the like, which is an oxide causing no problems with the oxidation, is effective though the barrier layer mentioned above can be applied.
As for a technique for film formation of the lower electrode 7, a variety of techniques such as a sputtering method, a vacuum deposition method, an MOCVD (Metal Organic Chemical Vapor Deposition) method can be appropriately used, however a sputtering method, where parameter for film growth can be set in a wide range, is preferable from the standpoint of orientation control and stress control.
As for a technique for film formation of a perovskite-type metal oxide film that is used as the variable resistor 8, a sputtering method is used.
Next, a memory cell configuration which is provided with two variable resistive elements 10a and 10b as illustrated in
In the memory cell configuration illustrated in
In the case where the film forming temperature of the PCMO film 8 is set at 420° C. or less, the PCMO film ends up being annealed at a temperature for depositing interlayer insulators and in heat treatment of H2 sintering causing the initial resistance value of the PCMO film to be changed. As shown in
Next, an example of the configuration wherein memory cells, each of which is the same as the variable resistive element 10 that is fabricated in the above-described process, are arranged in array form so that a memory array 101 can be formed as the inventive device 100, which is a nonvolatile semiconductor memory device having a large capacity, is described with reference to the drawings.
As described above, a memory cell 20 is formed of a series circuit of a selective transistor 6 and a variable resistive element 10 and thereby, the selective transistor 6 of the memory cell 20, which is selected by the potential of a word line, is turned ON and in addition, a program or erasure voltage is selectively applied to only the variable resistive element 10 of the memory cell 20 which has been selected by the potential of a bit line, and thereby, the resistance value of the variable resistor 8 in the variable resistive element 10 is changed in the configuration.
The block configuration that includes the peripheral circuits of the inventive device 100 shown in
The voltage switching circuit 109 supplies voltages to a word line, a bit line and a source line which are required at the time of readout, program and erasure of the memory array 101. Vcc indicates a supply voltage to the device, Vss indicates a ground voltage and Vpp indicates a voltage for program and erasure. In addition, data readout is carried out through the bit line decoder 105 and the readout circuit 107 from the memory array 101. The readout circuit 107 determines the condition of data and this result is sent to the control circuit 108 so as to be outputted to the data line 103.
Here, the block configuration of the inventive device 100 and the configuration of a memory cell illustrated in
As described above in detail, it becomes possible in a manufacturing method of a nonvolatile semiconductor memory device according to the present invention to fabricate nonvolatile memory elements using a low temperature process in the wiring process for a semiconductor integrated circuit and thereby, it becomes possible to provide a manufacturing process which prevents the wires from being thermally damaged and to fabricate nonvolatile memory elements in a semiconductor integrated circuit in the latter half of the manufacturing process so that an increase in the integration of nonvolatile memory elements due to a layered structure becomes possible and a design change of a semiconductor integrated circuit becomes easy.
Although the present invention has been described in terms of the preferred embodiments, it will be appreciated that various modifications and alterations might be made by those skilled in the art without departing from the spirit and scope of the invention. The invention should therefore be measured in terms of the claims which follow.
Number | Date | Country | Kind |
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JP2004-004949 | Jan 2004 | JP | national |