Source: https://patents.justia.com/patent/8350247
Timestamp: 2020-08-11 08:02:40
Document Index: 171543829

Matched Legal Cases: ['Application No. 10', 'Application No. 200710192709', 'Application No. 200710192709', 'Application No. 10', 'Application No. 08157323', 'Application No. 200610159882', 'Application No. 200810108832', 'Application No. 08157323', 'Application No. 10', 'Application No. 10']

US Patent for Resistive random access memory having a solid solution layer and method of manufacturing the same Patent (Patent # 8,350,247 issued January 8, 2013) - Justia Patents Search
Justia Patents With Specified Electrode Composition Or ConfigurationUS Patent for Resistive random access memory having a solid solution layer and method of manufacturing the same Patent (Patent # 8,350,247)
Nov 15, 2007 - Samsung Electronics
A resistive random access memory (RRAM) having a solid solution layer and a method of manufacturing the RRAM are provided. The RRAM includes a lower electrode, a solid solution layer on the lower electrode, a resistive layer on the solid solution layer, and an upper electrode on the resistive layer. The method of manufacturing the RRAM includes forming a lower electrode, forming a solid solution layer on the lower electrode, forming a resistive layer on the solid layer and forming an upper electrode on the resistive layer, wherein the RRAM is formed of a transition metal solid solution.
This application claims the benefit of Korean Patent Application No. 10-2006-0113385, filed on Nov. 16, 2006, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein in its entirety by reference.
Example embodiments relate to a resistive random access memory (RRAM) having a solid solution layer and method of manufacturing the same. Other example embodiments relate to a RRAM having a transition metal solid solution layer between an electrode and a resistive layer to stabilize voltage and resistance variations of the RRAM.
Conventionally, a semiconductor memory array structure includes memory cells, which are connected to one another. Each of the conventional memory cells of a dynamic random access memory (DRAM), which represents a semiconductor memory, includes a switch and a capacitor. DRAMs exhibit high integration and fast operating speed. If the power supply is removed from the DRAM, then all of the stored data is erased from the DRAM.
A flash memory represents a non-volatile memory capable of preserving stored data from being erased after the power supply is removed. Flash memories have non-volatile characteristics that are different than a volatile memory. Flash memories have a lower degree of integration and a slower operating speed than a DRAM.
Examples of a non-volatile memory, which have been studied, include a magnetic RAM (MRAM), a ferroelectric RAM (FRAM), a phase-change RAM (PRAM), etc.
MRAMs and FRAMs have been the focus of recent research. MRAMs store data according to the change in the polarization direction of a tunnel junction. FRAMs store data using polarization characteristics of a ferroelectric layer. MRAMs and FRAMs have higher integration, faster operating speeds and increased data retention characteristics. MRAMs and FRAMs may be driven at a lower power.
PRAMs store data according to a change in the resistance value caused by a phase change of a specific material. PRAMs include a resistor and a switch (transistor). If a method of manufacturing a conventional DRAM is used to manufacture the PRAM, then etching is difficult to perform. The additional time needed to etch may lower productivity and increase unit cost of PRAM products. As such, the competitive power of PRAMs may decrease.
A resistive RAM (RRAM) stores data according to a change in a variable resistance characteristic of a transition metal oxide (i.e., a resistance value varying according to voltage).
FIG. 1A is a diagram illustrating a cross-sectional view of a conventional RRAM using a conventional resistive transformation material having a conventional structure.
Referring to FIG. 1A, the conventional RRAM includes a lower electrode 11, a resistive layer 12 and an upper electrode 13, sequentially formed. The resistive layer 12 may be formed of a transition metal oxide. The lower and upper electrodes 11 and 13 may be formed of electrode materials used for a conventional semiconductor memory device.
FIG. 1B is a graph illustrating a relationship between a voltage V applied to the lower and upper electrodes 11 and 13 and a current I flowing in the resistive layer 12. The resistive layer 12 may be formed of a transition metal oxide as described above.
Referring to FIG. 1B, the voltage V was gradually increased from 0V in order to measure variations in the current flowing in the resistive layer 12. The current flowing in the resistive layer 12 gradually increases for an applied voltage between 0V and about 1V. The current flowing in the resistive layer 12 decreases in response to an increase in resistance at a voltage V of about 1V. The current flowing in the resistive layer 12 increases in response to a further increase of the voltage V. A higher resistance state of the resistive layer 12 refers to a reset state and a lower resistance state of the resistive layer 12 refers to a set state.
In FIG. 1B, the voltage applied when the set state changes into the reset state is referred to as a reset voltage RV. The reset voltage is within a range between about 0.6V and 1.2V. The highest value of a resistance SR in the set state may be 10 or more times greater than the lowest value of a resistance SR in the set state. A set voltage SV, which is applied when the reset state changes into the set state, may be within a range between 1.5V and 4.6V. As such, the set voltage SV may have a higher variation value.
As described above, the voltage and the resistance variations of the conventional RRAM are higher due to an unstable resistance level of the resistive layer 12. Reliability of the conventional RRAM decreases due to unstable set and reset voltages, etc.
Example embodiments relate to a resistive random access memory (RRAM) having a solid solution layer and method of manufacturing the same. Other example embodiments relate to a RRAM having a transition metal solid solution layer formed between an electrode and a resistive layer to stabilize voltage and resistance variations of the RRAM.
Example embodiments also provide a resistive random access memory (RRAM) including a resistance variation material to stabilize a reset current and a set voltage and a method of manufacturing the RRAM.
According to example embodiments, there is provided a RRAM having a transition metal solid solution wherein the RRAM includes a lower electrode, a solid solution layer on the lower electrode, a resistive layer on the solid layer and an upper electrode on the resistive layer.
The resistive layer may be formed of a transition metal oxide. The transition metal oxide may include NiO, TiO, HfO, ZrO, ZnO, WO, CoO, NbO and combinations thereof. The transition metal of the resistive layer may be Ni.
The solid solution layer may be a transition metal solid solution. The solid solution layer may include Al, Hf, Zr, Zn, W, Co, Au, Pt, Ru, Ir, Ti and combinations thereof. The solid solution layer may be formed by solidification (or solidifying) of a transition metal of the resistive layer into one selected from the group consisting of Al, Hf, Zr, Zn, W, Co, Au, Pt, Ru, Ir, Ti and combinations thereof.
According to example embodiments, there is provided a method of manufacturing a RRAM using a transition metal solid solution, which includes forming a lower electrode, forming a solid solution layer on the lower electrode, forming a resistive layer on the solid layer and forming an upper electrode on the resistive layer.
A transition metal alloy target may be formed (or deposited) on the lower electrode using sputtering to form the solid layer. Transition metal targets may be formed (or deposited) on the lower electrode using co-sputtering to form the solid layer.
The pressure of the gas in the process chamber may be controlled during the formation of the resistive layer to form the solid layer. The pressure of the gas may be in a range between 0.1 mTrr and 3 mTrr.
FIG. 1A is a diagram illustrating a cross-sectional view of a conventional resistive random access memory (RRAM) including a resistance variation material having a conventional structure;
FIG. 1B is a graph illustrating variations of in current with respect to a voltage applied to the conventional RRAM of FIG. 1A;
FIG. 2A is a diagram illustrating a cross-sectional view of a RRAM having a transition metal solid solution layer according to example embodiments;
FIG. 2B is a diagram illustrating a cross-sectional view of a RRAM having a transition metal solid solution layer according to example embodiments;
FIG. 3 is a diagram illustrating a cross-sectional view of a RRAM having a transition metal solid solution layer and formed on a transistor structure according to example embodiments;
FIG. 4 is a graph illustrating a resistance characteristic with respect to variations of a partial pressure of oxygen of NiO according to example embodiments;
FIG. 5 is a graph illustrating an X-ray diffraction (XRD) data of a solid solution layer formed by adjusting a partial pressure of vapor during the manufacturing of a RRAM including a transition metal solid solution layer according to example embodiments;
FIGS. 6A and 6B are graphs illustrating X-ray photoelectron spectroscopy (XPS) of a conventional RRAM and a RRAM according to example embodiments, respectively;
FIGS. 7A and 7B are graphs illustrating variations in the voltage of a conventional RRAM and a RRAM according to example embodiments, respectively;
FIGS. 8A and 8B are graphs illustrating variations in the resistance of a conventional RRAM and a RRAM according to example embodiments, respectively; and
FIG. 9 is a graph illustrating simplified electrical characteristics of a RRAM including a resistance variation material according to example embodiments.
Example embodiments relate to a resistive random access memory (RRAM) having a solid solution layer and method of manufacturing the same. Other example embodiments relate to a RRAM including a transition metal solid solution layer between an electrode and a resistive layer to stabilize voltage and resistance variations of the RRAM.
FIG. 2A is diagram illustrating a cross-sectional view of a RRAM having a transition metal solid solution layer according to example embodiments.
Referring to FIG. 2A, a solid solution layer 24 is formed on a lower electrode 21. A resistive layer 22 and an upper electrode 23 are sequentially formed on the solid solution layer 24. The lower and upper electrodes 21 and 23 may be formed of electrode materials used for a semiconductor device (e.g., Al, Hf, Zr, Zn, W, Co, Au, Pt, Ru, Ir, Ti, etc.). The resistive layer 22 may be formed of a material used for a conventional RRAM (e.g., transition metal oxide). For example, the resistive layer 22 may be formed of at least one selected from the group consisting of NiO, TiO2, HfO, ZrO, ZnO, WO3, CoO, CuO, Nb2O5 and combinations thereof. The thickness of the resistive layer 22 may be selectively adjusted within a range between 5 nm and 500 nm.
According to example embodiments, the RRAM includes the solid solution layer 24 between the lower electrode 21 and the resistive layer 22. The solid solution layer 24 may be formed of a transition metal solid solution. The solid solution layer 24 may be formed of a solid solution, which is formed by solidification of (or solidifying) a transition metal of the resistive layer 22 into at least one of Al, Hf, Zr, Zn, W, Co, Au, Pt, Ru, Ir, Ti and combinations thereof. If the resistive layer 22 is formed of NiO, then the solid solution layer 24 may be formed of a compound which is formed by solidification of Ni into at least one of Al, Hf, Zr, Zn, W, Co, Au, Pt, Ru, Ir, Ti and combinations thereof. The solid solution layer 24 may be formed having a thickness between 5 nm and 40 nm.
FIG. 2B is a diagram illustrating a cross-sectional view of a RRAM having a transition metal solid solution layer according to example embodiments.
Referring to FIG. 2B, a solid solution layer 24 may be formed on the lower electrode 21. The solid solution layer 24 may have a wave structure including areas A protruding into the resistive layer 22. The areas A may be a current path through which a current flows if a voltage is applied between the lower electrode 21 and the upper electrode 23. Referring to the RRAM in FIG. 1A, if a voltage is applied to the lower electrode 21 and the upper electrode 23, then a current path is changed and the RRAM exhibits a stable resistance characteristic. Referring to the RRAM in FIG. 2B, the areas A are formed in the solid solution layer 24. As such, a portion of the solid solution layer 24 has an area with a reduced distance from the upper electrode 23. A current path forms that allows for a more stable measurement of a resistance characteristic of the RRAM.
The RRAM of FIG. 2A is driven as a 1S (Switch)-1R (Resistance) structure connected to a switch structure (e.g., a transistor or a diode).
FIG. 3 is a diagram illustrating a cross-sectional view of a 1T (Transistor)-1R (Resistance) structure of a RRAM including a transition metal solid solution layer wherein the RRAM is connected to a transistor structure according to example embodiments.
Referring to FIG. 3, a source 202 and a drain 203 may be formed in a substrate 201. A gate structure including a gate insulating layer 204 and a gate electrode layer 205 may be formed on the substrate. The gate structure contacts the source 202 and the drain 203. An interlayer insulating layer 206 may be formed on the substrate 201. The interlayer insulating layer 206 may be formed on (or covering) the gate structure. A contact plug 207 may be formed on the source 202 or the drain 203 penetrating the interlayer insulating layer 206. The contact plug 207 is electrically connected to the lower electrode 21 of the RRAM including the transition metal solid solution. According to example embodiments, the RRAM may be connected to a diode structure having a p-type semiconductor layer and an n-type semiconductor layer.
A method of manufacturing the RRAM having a transition metal solid solution layer will now be described. According to example embodiments, the RRAM may be manufactured by sputtering, atomic layer deposition (ALD), chemical vapor deposition (CVD) or similar methods.
The lower electrode 21 may be formed of a conductive material. The lower electrode 21 may be formed of a transition metal (e.g., Al, Au, Pt, Ru, Ir, Ti or the like).
The solid solution layer 24 may be formed on the lower electrode 21. The solid solution layer 24 may be formed by at least three methods.
In a first method of forming the solid solution layer 24, a solid alloy may be formed on the lower electrode 21. If the solid solution layer 24 is formed using reactive sputtering, then an alloy target of Pt and Ni having an adjusted composition ratio may be sputtered to form the solid solution layer 24 on the lower electrode 21.
In a second method of forming the solid solution layer 24, materials for forming the solid solution layer 24 may be co-sputtered using individual targets to form the solid solution layer 24 on the lower electrode 21.
In a third method of forming the solid solution layer 24, the solid solution layer 24 may be formed during the formation of the resistive layer 22. If the solid solution layer 24 is formed of a Pt and Ni solid alloy, then the lower electrode 21 may be formed of Pt followed by the deposition of NiO to form the resistive layer 22. A pressure of a gas including oxygen in a process chamber may be adjusted within a range between 0.1 mTorr and 3 mTorr. Pt present on a surface of the lower electrode 21 may react with Ni to form the solid solution layer 24 on the lower electrode 21.
If the pressure of the gas including oxygen in the process chamber is adjusted to be within the range between 0.1 mTorr and 3 mTorr, then the supply of oxygen decreases. Ni reacts with Pt to form the solid solution layer 24 on the surface of the lower electrode 21.
The resistive layer 22 may be formed on the solid solution layer 24. A partial pressure of oxygen may be adjusted to form the resistive layer 22 of a transition metal oxide.
FIG. 4 is a graph illustrating variations of a resistance with respect to a partial pressure of oxygen in a mixture of an inactive gas and oxygen according to example embodiments.
Referring to FIG. 4, if the partial pressure of oxygen is low (see region A), then a metal characteristic similar to Ni develops. If the partial pressure of oxygen is gradually increased from 2.5% to 10% (see region B), then a resistance of NiO increases and a memory switching characteristic develops. If the partial pressure of oxygen is increased to 0.10% or more (see region C), then the resistance of Ni oxide gradually decreases and a threshold switching characteristic develops. If a thin film is manufactured, the same transition metal may be deposited on a sample using sputtering or likewise. The amount of oxygen supplied into a reaction chamber may be adjusted to manufacture the thin film in-situ. Transition metal oxides may show similar characteristics as NiO.
FIG. 5 is a graph illustrating X-ray diffraction (XRD) data of a solid solution layer of a RRAM manufactured according to example embodiments. The solid solution layer 24 in FIG. 5 was formed by adjusting a pressure in a process chamber during the formation of the resistive layer 22. The pressure in the process chamber was set within a range between 1.5 mT and 5 mT during direction current (DC) and radio frequency (RF) sputtering.
Referring to FIG. 5, if the pressure in the process chamber is set to 1.5 mT to form the solid solution layer 24, then a Pt/Ni solid layer is formed and a peak related to the Pt/Ni solid layer occurs. If the pressure in the process chamber is set to 5 mT, then the peak related to the Pt/Ni solid layer does not occur.
FIG. 6A is a graph illustrating an X-ray photoelectron spectroscopy (XPS) analysis of a conventional RRAM. FIG. 6B is a graph illustrating an XPS analysis of a RRAM having a solid solution layer formed according to example embodiments.
Referring to FIG. 6A, NiO and Ni are present at about the same signal level.
Referring to FIG. 6B, Ni is observed at a higher signal level than NiO. As such, Ni may exist under the resistive layer 22 and may be included in the solid solution layer 24.
FIG. 7A is a graph illustrating variations of the voltage with respect to the number of operation cycles of a conventional RRAM. FIG. 7B is a graph illustrating variations of the voltage with respect to the number of operation cycles of a RRAM having a solid solution layer formed according to example embodiments.
Referring to FIG. 7A, variations in set and reset voltages may be large. The variation in the set voltage may be substantially larger. As such, the number of operations required to manufacture the RRAM may increase, lowering the reliability of the conventional RRAM. Referring to FIG. 7B, the stability of the set and reset voltages increase.
FIG. 8A is a graph illustrating variations the resistance with respect to the number of operation cycles of a conventional RRAM. FIG. 8B is a graph illustrating variations of resistance with respect to the number of operation cycles of a RRAM including a solid solution layer formed according to example embodiments.
Referring to FIGS. 8A and 8B, the variations in the resistance of the RRAM according to example embodiments is substantially lower than the conventional RRAM.
FIG. 9 is a graph illustrating operational characteristics of a RRAM according to example embodiments. In FIG. 9, the horizontal axis denotes an applied voltage and the vertical axis denotes the change (or variations) in a current with respect to the applied voltage.
Referring to FIG. 9, if a voltage is gradually increased from 0V, then the current is increased in proportion to the voltage as shown in region G1 of the graph. If a voltage greater than a voltage V1, but less than a voltage V2 is applied, then a resistance of the RRAM increases and the current decreases as shown in region G3 of the graph. If a voltage V2 greater the voltage V1 (V2>V1) is applied, then the resistance is decreases and current increases as shown in region G1 of the graph.
The electrical characteristics of the RRAM may be affected if a voltage lower than the voltage V1 is applied in response to the intensity of a voltage greater than the voltage V1. For example, if the voltage between the voltages V1 and V2 is applied to the RRAM and the voltage less than the voltage V1 is applied, then a current as shown in region G2 of the graph of FIG. 9 is observed. If a voltage V3 greater than the voltage V2 is applied to the RRAM and the voltage less than the voltage V1 is applied, then a current as shown in region G1 of the graph of FIG. 9 is observed. As such, an intensity of a voltage applied within a range greater than the voltage V1 affects the electrical characteristics of the RRAM.
According to example embodiments, a transition metal oxide may be used as a RRAM applied as a multi-layer film having a resistance gradient. For example, the state of a RRAM having a voltage between V1 and V2 applied thereto may be designated as “0” and the state of the RRAM having a voltage greater than V2 applied thereto may be designated as “1” in order to record data. If data is reproduced, then the voltage less than V1 is applied to the RRAM to measure a drain current Id in order to check whether stored data is in a state of “0” or “1.” As such, the states of “1” and “0” may be selectively designated.
A reset voltage V1 and a set voltage V2 depending on an increase in the number of operations are constant in order to use a RRAM according to example embodiments and a set resistance is constant. The set voltage, the reset voltage and the resistance are constant in a RRAM using a transition metal solid solution according to example embodiments as shown in FIGS. 7B and 8B, producing a more stable RRAM.
As described above, in a RRAM and a method of manufacturing the RRAM according to example embodiments, the set voltage, the reset voltage and the resistance may be stabilized while operating the RRAM. As such, a more reliable RRAM may be manufactured. A solid layer may be more easily formed using an additional manufacture process while forming a resistive layer. Information may be stored and reproduced using the method. The RRAM according to example embodiments may operate at a higher speed.
a lower electrode including a first transition metal;
a solid solution layer on the lower electrode;
a resistive layer on the solid solution layer, the resistive layer including a second transition metal; and
wherein the solid solution layer is a transition metal alloy composed of a solidification of the second transition metal of the resistive layer and the first transition metal of the lower electrode, and
wherein the solid solution layer includes areas that protrude into the resistive layer.
2. The RRAM of claim 1, wherein the resistive layer is formed of a transition metal oxide.
3. The RRAM of claim 2, wherein the transition metal oxide includes at least one selected from the group consisting of NiO, TiO2, HfO, ZrO, ZnO, WO3, CoO, CuO, Nb2O5 and combinations thereof.
4. The RRAM of claim 1, wherein the solid solution layer includes at least one selected from the group consisting of Al, Hf, Zr, Zn, W, Co, Au, Pt, Ru, Ir, Ti and combinations thereof.
5. The RRAM of claim 1, wherein the first transition metal of the lower electrode is at least one selected from the group consisting of Al, Hf, Zr, Zn, W, Co, Au, Pt, Ru, Ir, Ti and combinations thereof.
6. The RRAM of claim 1, wherein the second transition metal of the resistive layer is Ni.
7. A method of manufacturing a resistive random access memory (RRAM), comprising:
forming a lower electrode including a first transition metal;
forming a solid solution layer on the lower electrode;
forming a resistive layer on the solid solution layer, the resistive layer including a second transition metal; and
forming an upper electrode on the resistive layer,
wherein forming the solid solution layer includes forming a transition metal alloy by solidifying the second transition metal of the resistive layer and the first transition metal of the lower electrode, and
wherein forming the solid solution layer includes forming areas that protrude into the resistive layer.
8. The method of claim 7, further comprising controlling a pressure of a gas in a process chamber while forming the resistive layer.
9. The method of claim 8, wherein the pressure of the gas is within a range of 0.1mTrr and 3mTrr.
10. The method of claim 8, wherein the second transition metal of the resistive layer is Ni.
11. The method of claim 7, wherein the first transition metal of the lower electrode is at least one selected from the group consisting of Al, Hf, Zr, Zn, W, Co, Au, Pt, Ru, Ir, Ti and combinations thereof.
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Patent Publication Number: 20080116438
Inventors: Myoung-jae Lee (Suwon-si), Young-soo Park (Yongin-si), Ran-ju Jung (Suwon-si), Sun-ae Seo (Hwaseong-si), Dong-chul Kim (Suwon-si), Seung-eon Ahn (Suwon-si)
Assistant Examiner: Yu-Hsi D Sun
Application Number: 11/984,277
Current U.S. Class: With Specified Electrode Composition Or Configuration (257/4); Systems Using Particular Element (365/129); Resistive (365/148); Static Random Access Memory, Sram, Structure (epo) (257/E27.098); Memory Effect Devices (epo) (257/E29.17); Memory Structures (epo) (257/E21.613); Bulk Effect Device (257/1); Bulk Effect Switching In Amorphous Material (257/2); With Means To Localize Region Of Conduction (e.g., "pore" Structure) (257/3); In Array (257/5)