This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2011-208208, filed on Sep. 22, 2011, the entire contents of which are incorporated herein by reference.
The embodiments described herein relate to a nonvolatile semiconductor memory device and a method of manufacturing the same.
Flash memory in which memory cells having a floating gate structure are NAND connected or NOR connected to configure a cell array is well known as a conventional electrically rewritable nonvolatile memory. In addition, ferroelectric memory is also known as a nonvolatile memory capable of being accessed randomly at high speed.
At the same time, resistance varying type memory that uses a variable resistance element for a memory cell is proposed as a technology for achieving further miniaturization of memory cells. The following are known as variable resistance elements, namely: a phase change memory element that has its resistance value changed by a change in state of crystallization/amorphousness of a chalcogenide compound; an MRAM element that employs resistance change due to a tunnel magneto-resistance effect; a polymer ferroelectric RAM (PFRAM) element that has a resistance element formed by a conductive polymer; a ReRAM element that has resistance change caused by an electrical pulse application; and so on.
Of these, the variable resistance elements used in ReRAM are broadly divided into those in which resistance change occurs due to presence/absence of charge trapped in a charge trap existing in an electrode interface, and those in which resistance change occurs due to presence/absence of a conductive path induced by oxygen deficiency or the like.
Moreover, there are two kinds of operation modes in the variable resistance elements used in ReRAM. One sets a high-resistance state and a low-resistance state by switching a polarity of an applied voltage, and this is called a bipolar type. The other allows a high-resistance state and a low-resistance state to be set by controlling a voltage value and a voltage application time without switching a polarity of an applied voltage, and this is called a unipolar type.
Even further miniaturization and increased storage capacity is expected from these kinds of variable resistance elements acting as cross-point type memory cells, hence increasingly low-power data write is desired.
A nonvolatile semiconductor memory device according to an embodiment comprises memory cells in each of which are series-connected: a variable resistance element including a metal oxide; an electrode including a polysilicon layer and a SiGe layer formed between the polysilicon layer and the metal oxide; and a bipolar type current rectifying element.
Embodiments of the nonvolatile semiconductor memory device are described below with reference to the drawings.
[Overall Configuration]
Electrically connected to bit lines BL of the memory cell array 1 is a column control circuit 2 for controlling the bit lines BL of the memory cell array 1 and enabling data erase of the memory cells MC, data write to the memory cells MC, and data read from the memory cells MC. Moreover, electrically connected to word lines WL of the memory cell array 1 is a row control circuit 3 for selecting the word lines WL of the memory cell array 1 and enabling data erase of the memory cells MC, data write to the memory cells MC, and data read from the memory cells MC.
[Memory Cell Array]
[Memory Cell]
As shown in
The upper electrode TE and the barrier metals BM1 and BM2 in the present embodiment are formed from a TiN layer. This TiN layer can be formed by a method such as sputtering, and functions as a barrier metal layer and adhesive layer. Note that the upper electrode TE and the barrier metals BM1 and BM2 may also be formed by other metals such as Ti or the like.
The variable resistance element VR is formed by a HfOx layer of about 5 nm acting as a resistance varying film. A TiOx layer of about 8 Å is formed in a boundary between the HfOx layer and the upper electrode TE formed from TiN. Of these, the HfOx layer can be formed by a method such as ALD (Atomic Layer Deposition). Note that a film thickness of the HfOx layer is not limited to about 5 nm, but maybe changed appropriately in a range of about 2-10 nm. Moreover, in the present embodiment, HfOx is employed as the resistance varying film, but the following may also be adopted as the resistance varying film, namely, oxides of, for example, chromium (Cr), tungsten (W), vanadium (V) , niobium (Nb), tantalum (Ta), titanium (Ti), zirconium (Zr), hafnium (Hf), scandium (Sc), yttrium (Y), thorium (Tr), manganese (Mn), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), nickel (Ni) , copper (Cu) , zinc (Zn) , cadmium (Cd), aluminum (Al), gallium (Ga) , indium (In), tin (Sn) , lead (Pb), bismuth (Bi) , or oxides of, for example, the so-called rare earth elements from lanthanum (La) to lutetium (Lu), and so on.
In addition, the lower electrode BE is formed from an n type polysilicon layer and a SiGe layer formed in a boundary between this polysilicon layer and the HfOx layer. In the example shown in
In addition, the current rectifying element Di is formed as a NIP layer from an upper layer. Note that in the present embodiment, a diode is employed as the current rectifying element Di, but other ohmic elements such as a transistor may also be used.
[Operation of Memory Cell]
The nonvolatile semiconductor memory device according to the present embodiment is of a so-called bipolar type. Therefore, write of data to the memory cell MC is performed by applying for a certain time to a selected one of the memory cells MC a voltage corresponding to a breakdown voltage in a reverse direction of the current rectifying element Di. As a result, the variable resistance element VR in the selected memory cell MC changes from a high-resistance state to a low-resistance state. Hereinafter, this operation for changing the variable resistance element VR from a high-resistance state to a low-resistance state is called a “setting operation” . On the other hand, erase of data in the memory cell MC is performed by applying for a certain time to the variable resistance element VR in a low-resistance state after the setting operation a certain voltage in a forward direction of the current rectifying element Di. As a result, the variable resistance element VR changes from a low-resistance state to a high-resistance state. Hereinafter, this operation for changing the variable resistance element VR from a low-resistance state to a high-resistance state is called a “resetting operation”. For example, in the case of binary data storage, performing the resetting operation and setting operation on the selected memory cell MC is performed by changing a resistance state of the variable resistance element VR in the selected memory cell MC to a high-resistance state and low-resistance state, respectively. Moreover, forming needs to be performed on the variable resistance element VR when the variable resistance element VR is to be used. Forming also is performed by continuing to apply a certain voltage for a certain time, similarly to in the setting operation and resetting operation.
In the memory cell array 1 having the three-dimensional stacked arrangement as shown in
[Operation Model of Variable Resistance Element]
Next, an operation model of bipolar type ReRAM is described.
That is, as shown in
That is, the variable resistance element VR immediately after forming is in a low-resistance state (set state), but, by performing the resetting operation, changes to a high-resistance state (reset state). The resetting operation is performed by applying a voltage between the upper electrode TE and the lower electrode BE, setting the lower electrode BE to a high potential. As shown in
Moreover, the setting operation is performed, contrarily to the resetting operation, by applying a voltage between the upper electrode TE and the lower electrode BE, setting the upper electrode TE to a high potential. As shown in
[Setting Voltage]
The reason why a setting voltage in the comparative example is high and the reason why a setting voltage in the nonvolatile semiconductor memory device according to the present embodiment can be reduced are explained below based on the above-described operation model.
The lower electrode BE made of Si is formed by, for example, crystallizing-annealing, at about 650° C., Si and dopants formed by reduced pressure CVD or the like, but at a film thickness of 30 nm or less, there is a low probability that a nucleus for crystallization exists, and this results in insufficient crystallization and an increased resistance value. Therefore, voltage drop in a lower electrode BE portion increases and a voltage applied to the variable resistance element VR is reduced, and this is a first reason why the setting voltage is high.
In addition, the comparative example is configured such that the boundary between the variable resistance element VR and the lower electrode BE is formed by Si, the resetting operation causes SiOx to be formed in the switching boundary SW, and the setting operation causes oxygen to be withdrawn from the SiOx of the switching boundary SW. However, since SiOx is stable, it is difficult to withdraw oxygen from the SiOx, and this is a second reason linked to an increase in the setting voltage.
The first reason can be resolved by adding Ge to the Si lower electrode BE. When Ge is added to the Si, crystallization improves, hence the resistance value is reduced along with the added amount of Ge. However, there is a problem that if too much Ge is added to the Si, part of the crystal grain undergoes abnormal growth, causing a localized deterioration in roughness of the SiGe layer surface.
In view of the above points, the present embodiment adopts the two layer structure of the polysilicon layer and the SiGe layer for the lower electrode BE. The polysilicon layer is formed independently as a uniform film even when having a film thickness of several tens of nm and the SiGe layer is an extremely thin film (for example, 2 nm), hence these layers are capable of being formed as uniform well-crystallized films, without the crystal grain undergoing abnormal growth. Moreover, forming the SiGe layer in a layer above the polysilicon layer and then performing crystallizing-annealing enables crystallization of the polysilicon layer to be promoted while suppressing abnormal growth, and enables the resistance value of the entire lower electrode BE including the polysilicon layer and the SiGe layer to be lowered. Employing such a low-resistance electrode also enables voltage drop in the lower electrode BE during a write operation to be suppressed, thereby enabling lowering of setting voltage and suppression of resetting voltage increase.
In addition, the second reason is improved as below. That is, in the present embodiment, the SiGe layer exists in the boundary between the variable resistance element VR and the lower electrode BE acting as the positive electrode in the resetting operation, hence the resetting operation causes GeO2 and GeO to be formed in addition to SiOx.
Now, Gibbs standard generated energy at 1000K for Hf02, SiO2, Ge02, and GeO is, respectively, −895 kJ/mol, −726.9 kJ/mol, −397.1 kJ/mol, and −105.7 kJ/mol, making it clear that GeO2 and GeO are unstable substances compared to SiO2 and HfO2. This means that reducing GeO2 and GeO is easy, that is, requires only a low energy, compared to reducing SiO2. By thus providing SiGe between the variable resistance element VR and the lower electrode BE in this way, the present embodiment enables the setting voltage to be lowered.
When SiGe is employed as the lower electrode, the setting voltage decreases, and at the same time the resetting voltage increases. However, because in the resetting operation a voltage is applied to the memory cell MC in the forward direction, voltage drop in the current rectifying element Di is comparatively small. Therefore, the rise amount of the resetting voltage is small compared to the reduction amount of the setting voltage with respect to the comparative example, hence operating electric power of the nonvolatile semiconductor device overall is reduced.
Moreover, in the present embodiment, although GeO2 and GeO are thought to be formed in the switching boundary SW during the resetting operation, GeO2 and GeO have a small Gibbs standard generated energy and are thus unstable substances compared to SiO2, as mentioned above. Therefore, the possibility of a memory cell MC in a set state attaining a reset state regardless of the resetting operation not being performed in said memory cell MC is reduced, and data retention (data retaining characteristic) is thus improved.
Furthermore, in the nonvolatile semiconductor memory device according to the present embodiment, variations in setting voltage and resetting voltage are reduced compared to a conventional example. The reason for this is not understood at present, but it is thought to be due to an oxidation/reduction reaction becoming easier and improvement in crystallization.
[Method of Manufacturing]
Next, a method of manufacturing a nonvolatile semiconductor memory device according to the present embodiment is described. As shown in
Next, as shown in
Next, as shown in
Note that only the memory cell MC1 layer portion is described in
[Other]
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 methods and systems described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the methods and systems 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 |
---|---|---|---|
2011-208208 | Sep 2011 | JP | national |