This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2010-231293, filed on Oct. 14, 2010; the entire contents of which are incorporated herein by reference.
Embodiments disclosed herein relate generally to a nonvolatile variable resistance element and a method of manufacturing the nonvolatile variable resistance element.
A NAND flash memory is widely spread as a storage device for large volume data. At present, a reduction in cost and an increase in capacity per bit are in progress by microminiaturizing a storage element. In future, it is requested to advance further miniaturization. However, to further miniaturize a flash memory, there are large number of problems that should be solved such as a short channel effect and suppression of cell-to-cell interference and performance fluctuation. Therefore, it is expected that a new storage device replacing a floating-gate type flash memory is put to practical use.
Recently, a two-terminal nonvolatile variable resistance element represented by a ReRAM (Resistive Random Access Memory) is actively developed. This element is a prospective candidate as a large-capacity storage device in the next generation replacing the floating gate flash memory in terms of the fact that a low-voltage operation, high-speed switching, and microminiaturization are possible. Above all, a memory including amorphous silicon as a variable resistance layer attracts attention because of a high switching yield and possibility of microminiaturization.
To realize a large-capacity storage device using such a two-terminal nonvolatile variable resistance element, in some case, a so-called stacked cross point structure is adopted. In this case, a thermal history applied to each of variable resistance elements during a manufacturing process for a storage device depends on in which layer the variable resistance element is present. Therefore, when the variable resistance element has relatively weak thermal resistance, it is likely that a characteristic of the element changes according to the thermal history. This causes characteristic fluctuation in the element.
In particular, when amorphous silicon is used as a variable resistance film, it is feared that a phase change from an amorphous structure to a polycrystalline structure is caused depending on a thermal history. An element characteristic substantially changes because of a volume change and a conductivity change involved in the phase change.
Patent Document 1 US2010/0085798
In general, according to one embodiment, a first electrode, a second electrode, and a variable resistance layer are provided. The variable resistance layer is arranged between the first electrode and the second electrode and contains a polycrystalline semiconductor as a main component.
Exemplary embodiments of nonvolatile variable resistance elements and methods of manufacturing the nonvolatile variable resistance elements will be explained below in detail with reference to the accompanying drawings. The present invention is not limited to the following embodiments.
In
When the polycrystalline semiconductor of the variable resistance layer 3 is polysilicon, impurity-doped silicon can be used as the first electrode 1. For example, high-concentration B ion can be implanted in silicon such that the resistivity of the first electrode 1 is equal to or lower than 0.005 Ωcm. The second electrode 2 is an electrode containing metal. For example, Ag can be used as the second electrode 2. Other conductive materials can be used as the first electrode 1 and the second electrode 2. For example, Ag, Au, Ti, Ni, Co, Al, Fe, Cr, Cu, W, Hf, Ta, Pt, Ru, Zr, or Ir, or nitride or carbide of the metal, or the like can be used as the first electrode 1 and the second electrode 2. An alloy material containing a plurality of kinds among these metals and semiconductor elements can also be used as the first electrode 1 and the second electrode 2. The first electrode 1 and the second electrode 2 can contain the same metal.
In
In
For example, in the low-resistance state, the metal of the second electrode 2 intrudes into the variable resistance layer 3 and forms metal filaments 11. On the other hand, in the high-resistance state, the metal filaments 11 that intrude into the variable resistance layer 3 are collected by the second electrode 2. The metal filaments 11 formed in the variable resistance layer 3 are eliminated. The nonvolatile variable resistance element can store data for one bit by reversibly transitioning between these two states according to voltage application.
In
In the low-resistance state, in a range in which the voltage Vtop is smaller than the set voltage Vset to some degree, the electric current Itop flows generally in proportion to the voltage Vtop (P2).
On the other hand, when the voltage Vtop is swept in a negative direction with respect to the nonvolatile variable resistance element in the low-resistance state, the electric current Itop suddenly decreases at a reset voltage Vreset (near −2.5 volts) and the nonvolatile variable resistance element transitions from the low-resistance state to the high-resistance state (P3).
In the high-resistance state, in a range in which the voltage Vtop is larger than the reset voltage Vreset to some degree, the electric current Itop hardly flows with respect to the voltage Vtop (P4).
When the voltage Vtop is further swept in the positive direction from this state (P1), the electric current Itop suddenly increases at the set voltage Vset and the nonvolatile variable resistance element transitions from the high-resistance state to the low-resistance state. In other words, this nonvolatile variable resistance element can store data for one bit by reversibly transitioning between the high-resistance state and the low-resistance state.
A method of manufacturing the nonvolatile variable resistance element shown in
In
Subsequently, polysilicon is deposited on the first electrode 1 by, for example, a chemical vapor deposition (CVD) method, whereby the variable resistance film 3 is formed on the first electrode 1. Film formation conditions for the polysilicon are set such that the concentration of hydrogen contained in the polysilicon is equal to or higher than 1019 cm−3.
For example, as film formation conditions by an LP-CVD (Low Pressure Chemical Vapor Deposition) method, a material gas is SiH4 and a flow rate and pressure can be respectively set to 100 sccm and 0.1 Torr. Film formation temperature can be set to 620° C. In the case of such film formation conditions, deposition speed of the polysilicon is 9 nm/min.
When silane gas SiH4 or disilane gas Si2H6 alone is used as the material gas during film formation, to keep the concentration of hydrogen contained in the polysilicon layer at concentration equal to or higher than 1019 cm−3, it is desirable that hydrogen present in the material gas does not remove during the film formation. Therefore, it is necessary to set the deposition speed as high as possible. For example, when temperature during the film formation is 620° C. and the film formation is performed at deposition speed equal to or higher than 9 nm/min, the hydrogen concentration can be kept at concentration equal to or higher than 1019 cm−3. In the case of this embodiment, the film thickness of the variable resistance layer is 150 nanometers. The film thickness of the variable resistance layer does not need to be 150 nanometers. Typically, the film thickness of the variable resistance layer is 1 nanometer to 300 nanometers. If microminiaturization of an element is taken into account, the film thickness is desirably smaller. However, if the film thickness is too small, a uniform film is not obtained. Therefore, the film thickness is more desirably 2 nanometers to 50 nanometers.
The temperature during the film formation does not always need to be 620° C. To deposit polysilicon containing hydrogen at concentration equal to or higher than 1019 cm−3, typically, it is desirable to set the film formation temperature to 600° C. to 700° C. and set the deposition speed to speed equal to or higher than 9 nm/min.
It is unnecessary to use silane or disilane alone as the material gas. Mixed gas of silane or disilane and hydrogen can be used as a material. In this case, as in the above case, the concentration of hydrogen contained in the polysilicon can be kept at concentration equal to or higher than 1019 cm−3.
A metal film is formed on the polysilicon film by a method such as sputtering or vapor deposition, whereby the second electrode 2 is formed on the variable resistance layer 3.
In the embodiment explained above, a method of depositing the polysilicon layer on the first electrode 1 at the film formation temperature equal to or higher than 600° C. is explained. However, after an amorphous silicon layer is formed on the first electrode 1 at film formation temperature lower than 600° C., the amorphous silicon layer can be changed to a polycrystalline semiconductor layer by subjecting the amorphous silicon layer to thermal treatment at temperature equal to or higher than 600° C.
In
In
It is possible to further improve thermal resistance of the nonvolatile variable resistance element by adding a very small amount of oxygen in the polycrystalline semiconductor. In particular, when impurity doped silicon is used as the first electrode 1, it is possible to suppress impurities from diffusing in the variable resistance layer 3′ and further improve reliability of a large-capacity storage device. According to the examination of the inventors, it is known that a thermal resistance improvement effect is obtained by adding oxygen by an amount equal to or larger than 1021 atoms/cm3.
A method of manufacturing the nonvolatile variable resistance element shown in
In
In this example, oxygen is used for the material gas. However, oxygen does not always need to be used for the material gas. NO gas or N2O gas can be mixed with silane gas. Because the variable resistance layer 3′ is deposited at deposition speed of 9 nm/min, a hydrogen content is equal to or larger than 1019 cm−3.
It is possible to suppress a grain diameter of the polysilicon by controlling the ratio of flow rates of silane gas and oxygen during film formation. To realize a large-capacity storage device, because microminiaturization of the nonvolatile variable resistance element is necessary, it is desirable that the grain diameter of the polysilicon is also smaller. Typically, the grain diameter of the polysilicon is 2 nanometers to 10 nanometers. From the viewpoint of suppressing characteristic fluctuation in the nonvolatile variable resistance element involved in the microminiaturization, it is more desirable that the grain diameter of the polysilicon is 2 nanometers to 5 nanometers. The grain diameter of the polysilicon indicates a maximum of crystal grains measured by Atom Probe.
In
When a hydrogen content of the polysilicon is small, the gaps are small even in the grain boundaries 4 and the activation energy necessary for movement of the metal Ag is large. Therefore, the metal filaments 11 are less easily formed in the variable resistance layers 3 or 3′.
In
In
As a result, as shown in
In the case of the polysilicon, electrons move by hopping in the grain boundaries 4. Therefore, when an electric current is large, this indicates that the electrons easily hop in the grain boundaries 4 and the gaps present in the grain boundaries 4 are small. It is seen that, when hydrogen in the polysilicon increases, a current flowing through the polysilicon decreases and the electrons less easily hop in the grain boundaries 4.
Further, when OH groups are present in grain boundaries into which a metal element intrudes, metal ion is easily formed by a reaction described below.
Ag+OH→Ag(OH)→Ag++OH−
When metal that forms the metal filament 11 is easily ionized through the above described reaction, this substantially contributes to improvement of the switching characteristic. Since elimination and generation of the metal filaments 11 composed of the metal element is controlled by applying voltage, it is desirable that the metal element is ionized. When a large number of OH groups are present in a moving path of the metal element, the metal element is easily ionized.
In
In
In
As the memory cell 23, for example, the nonvolatile variable resistance element shown in
When writing in a selected cell is performed, the set voltage Vset is applied to the lower wire 21 of a selected column and a ½ voltage of the set voltage Vset is applied to the lower wire 21 of unselected columns. 0 V is applied to the upper wire 24 of a selected row. The ½ voltage of the set voltage Vset is applied to the upper wire 24 of unselected rows.
As a result, the set voltage Vset is applied to the selected cell designated by the selected row and the selected column and writing in the selected cell is performed. On the other hand, because the ½ voltage of the set voltage Vset is applied to a half-selected cells designated by the unselected columns and the selected row, writing in the half-selected cells is not performed. Because, the ½ voltage of the set voltage Vset is applied to a half-selected cells designated by the selected column and the unselected rows, writing in the half-selected cells is not performed. Because 0 V is applied to an unselected cells designated by the unselected rows and the unselected columns, writing in the unselected cells is not performed. Therefore, it is possible to apply Vset only to the selected cell and perform writing in the selected cell.
When read out from the selected cell is performed, a ½ voltage of a read voltage Vread is applied to the lower wire 21 of the selected column and 0 V is applied to the lower wire 21 of the unselected columns. A −½ voltage of the read voltage Vread is applied to the upper wire 24 of the selected row and 0 V is applied the upper wire 24 of the unselected rows.
As a result, the read voltage Vread is applied to the selected cell designated by the selected row and the selected column and readout from the selected cell is performed. On the other hand, because the −½ voltage of the read voltage Vread is applied to the half-selected cells designated by the unselected columns and the selected row, readout from the half-selected cells is not performed. Because the ½ voltage of the read voltage Vread is applied to the half-selected cells designated by the selected column and the unselected rows, readout from the half-selected cells is not performed. Because 0 V is applied to the unselected cells designated by the unselected rows and the unselected columns, readout from the unselected cells is not performed.
When erasing in the selected cell is performed, the reset voltage Vreset is applied to the lower wire 21 of the selected column and a ½ voltage of the reset voltage Vreset is applied to the lower wiring 21 of the unselected columns. 0 V is applied to the upper wire 24 of the selected row and the ½ voltage of the reset voltage Vreset is applied to the upper wire 24 of the unselected rows.
As a result, the reset voltage Vreset is applied to the selected cell designated by the selected row and the selected column and erasing in the selected cell is performed. On the other hand, because the ½ voltage of the reset voltage Vreset is applied to the half-selected cells designated by the unselected columns and the selected rows, erasing in the half-selected cells is not performed. Because the ½ voltage of the reset voltage Vreset is applied to the half-selected cells designated by the selected column and the unselected rows, erasing in the half-selected cells is not performed. Because 0 V is applied to the unselected cells designated by the unselected rows and the unselected columns, erasing in the unselected cells is not performed.
In
A nonvolatile variable resistance element 23 is arranged on the semiconductor substrate 31 to be adjacent to the transistor 41. As the nonvolatile variable resistance element 23, for example, a configuration same as that shown in
The transistor 41 is turned on via the word line 36, whereby the nonvolatile variable resistance element 23 can be accessed and the nonvolatile variable resistance element 23 as a reading and writing target can be selected.
In the explanation of an example shown in
In
One ends of the nonvolatile variable resistance elements 23 in the same columns are connected to the same bit lines BL1 to BL3. One ends of the transistors 41 in the same rows are connected to the same source lines SL1 to SL3. Gate electrodes 35 of the transistors 41 in the same rows are connected to the same word lines WL1 to WL3.
The transistors 41 are turned on via the word lines WL1 to WL3, whereby a voltage can be applied between first electrodes 1 and second electrodes 2 of the nonvolatile variable resistance elements 23 in a selected row. Therefore, it is possible to prevent an electric current from flowing to the nonvolatile variable resistance elements 23 in an unselected rows during readout from the nonvolatile variable resistance elements 23 in the selected row. It is possible to reduce a readout time.
In
When forward bias is applied to the unipolar variable resistance element 57, it is possible to form the metal filaments 11 shown in
On the other hand, when reverse bias is applied to the unipolar variable resistance element 57, it is possible to eliminate the metal filaments 11 shown in
It is possible to achieve a high ON/OFF ratio by connecting the nonvolatile variable resistance element 23 in series to the unipolar variable resistance element 57 compared with an ON/OFF ratio achieved by connecting a diode in series to the unipolar variable resistance element 57.
In the explanation of an example shown in
In
One ends of the unipolar variable resistance elements 57 in the same columns are connected to the same bit lines BL1 to BL3. One ends of the nonvolatile variable resistance elements 23 in the same rows are connected to the same word lines WL1 to WL3.
By connecting the nonvolatile variable resistance elements 23 and the unipolar variable resistance elements 57 in this way, the resistance of the variable resistance elements is increased when reverse bias is applied to an unselected cell. Therefore, it is possible to reduce current noise flowing from the unselected cell during current readout from a selected cell, improve stability of a readout operation, and reduce a readout time.
While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel embodiments described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the embodiments described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.
Number | Date | Country | Kind |
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2010-231293 | Oct 2010 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP11/55162 | 2/28/2011 | WO | 00 | 5/16/2013 |