Simplified ZrTiO x -based RRAM cell structure with rectifying characteristics by integrating Ni/n + -Si diode
© Lin et al.; licensee Springer. 2014
Received: 29 March 2014
Accepted: 24 May 2014
Published: 30 May 2014
A simplified one-diode one-resistor (1D1R) resistive switching memory cell that uses only four layers of TaN/ZrTiO x /Ni/n+-Si was proposed to suppress sneak current where TaN/ZrTiO x /Ni can be regarded as a resistive-switching random access memory (RRAM) device while Ni/n+-Si acts as an Schottky diode. This is the first RRAM cell structure that employs metal/semiconductor Schottky diode for current rectifying. The 1D1R cell exhibits bipolar switching behavior with SET/RESET voltage close to 1 V without requiring a forming process. More importantly, the cell shows tight resistance distribution for different states, significantly rectifying characteristics with forward/reverse current ratio higher than 103 and a resistance ratio larger than 103 between two states. Furthermore, the cell also displays desirable reliability performance in terms of long data retention time of up to 104 s and robust endurance of 105 cycles. Based on the promising characteristics, the four-layer 1D1R structure holds the great potential for next-generation nonvolatile memory technology.
As conventional flash memory is approaching its scaling limits, resistive-switching random access memory (RRAM), one of the most promising emerging nonvolatile memories, holds the potential to replace it for future memory-hungry applications because of superior speed, higher density, and complementary metal-oxide-semiconductor (CMOS) compatibility [1–4]. For the last decade, although many dielectrics have shown resistive switching characteristics, undesirable cross-talk through neighboring cells due to sneak current leads to read disturbance and limits the array size. To circumvent the issue, series connection of one diode (1D) with one RRAM (1R) to form the so-called 1D1R cell has been proposed since the sneak current can be suppressed by the rectifying the characteristics without sacrificing the storage density. The requirements of the diode include large ratio between forward and reverse current (F/R ratio) under read operation, fab-friendly process, and many types of diodes were discussed in the literature. Metal-insulator-metal (MIM)-based diodes such as Pt/TiO2/Ti [5, 6], Pt/CoO/IZO/Pt , and Pt/TiO x /Pt  meet the requirement of high F/R ratio, however, the implementation of these diodes necessitates at least three layers and the adoption of high-work function Pt, increasing the complexity of integration and process cost respectively. Besides aforementioned diodes, W/TiO x /Ni-based MIM diode  is promising since it achieves F/R ratio larger than 1,000 without using Pt and successfully demonstrates the integration with bipolar RRAM. Nevertheless, three layers are still required to implement the diodes. Other types of diode include p-type/n-type oxide-based diodes such as NiO x /TiO x , CuO x /InZnO x , and NiO x /ITO x , or polymer film such as P3HT/n-ZnO . Even though high F/R ratio is achieved, most oxides are not compatible with incumbent ultra large scale integration (ULSI) technology. Diode based on p-type/n-type Si is another viable technology; although it has been integrated with phase change memory , related research on RRAM has not been reported. In addition, with top and bottom electrodes, these diodes require four layers to be implemented; thus, the issue of process complexity still remains. By integrating the aforementioned diodes with RRAM devices, process that needs more than four layers is indispensable.
Recently, without the need of a diode, RRAM devices with self-rectifying behavior have been widely developed because of the simpler process. For self-rectifying RRAM devices, dielectric and electrode should be carefully selected to concurrently meet the requirement of large F/R ratio for diode and high RHRS/RLRS ratio for RRAM where RHRS and RLRS respectively denote the resistance at high-resistance state (HRS) and low-resistance state (LRS). Most device structures with self-rectifying behavior such as Cu/a-Si/WO3/Pt , Pt/Al/PCMO/Pt , and Pt/ZrO x /HfO x /TiN/HfO x /ZrO x /Pt  still possess unsatisfactory RHRS/RLRS ratio (approximately 10) and F/R ratio (approximately 100). In addition, it usually requires at least four layers to implement self-rectifying characteristics for aforementioned RRAM devices and the structure compromises the advantage of simple process of self-rectifying devices. Ni/AlO x /n+-Si , a simpler structure with self-rectifying characteristics, exhibits desirable RHRS/RLRS and F/R ratio. However, forming voltage larger than 5 V is required, and there is room to improve the operation voltage which is higher than 2 V. In this work, a novel 1D1R cell structure based on TaN/ZrTiO x /Ni/n+-Si was proposed where TaN/ZrTiO x /Ni was employed as the resistive switching element and Ni/n+-Si played the role of Schottky diode. The reason to adopt ZrTiO x is that it has been shown to have desirable RRAM characteristics . Compared to those published in the literature, the intriguing points of this work lie in four aspects: (1) This is the first structure that uses metal/semiconductor Schottky diodes to rectify current characteristics and the whole structure requires only four layers which are much simpler than other 1D1R structures and even comparable to self-rectifying devices. (2) This 1D1R cell displays desirable electrical characteristics in terms of forming-free property, RHRS/RLRS ratio higher than 103, F/R ratio larger than 103, operation voltage close to 1 V, negligible resistance change up to 104 s retention time at 125°C, and robust endurance of 105 cycles. (3) Unlike some 1D1R structures that use special materials as diode, all the layers used in this work are fab-friendly and can be fully integrated with existing ULSI process.
N-type Si wafer with doping concentration of 2 × 1017 cm−3 was used as the starting material for 1D1R cell fabrication. A 35-nm Ni was initially deposited on the Si wafer as the bottom electrode of MIM-based RRAM device. Note that the Ni layer on the n-type Si substrate also formed the Schottky diode because of the metal/semiconductor junction. Next, a 10-nm oxygen-deficient ZrTiO x film was deposited by e-beam evaporation from a pre-mixed source that contains ZrO2 and Ti at room temperature as the resistance switching dielectric. TaN of 35 nm was then deposited and patterned by shadow mask as the top electrode. Finally, complete 1D1R cells with the structure of TaN/ZrTiO x /Ni/n+-Si were formed. For electrical characterization, voltage was applied on the top electrode with the grounded Si substrate. Separate RRAM (TaN/ZrTiO x /Ni) and Schottky diode (Ni/n+-Si) were also formed to evaluate the behavior of single device. Note that single RRAM devices were fabricated on SiO2 rather than Si substrate for better isolation so that pure RRAM performance can be measured. All the electrical data were measured by devices with the area of 250 μm × 250 μm. In addition to electrical analysis, transmission electron microscopy (TEM) and x-ray diffraction (XRD) were respectively used to characterize the interface property between Ni/n+-Si and to study the crystallinity of the switching dielectric ZrTiO x .
Results and discussion
Physical analysis of 1D and 1R structure
DC behavior for 1D, 1R, and 1D1R devices
The RESET current decreases to be around 10−5 A which is two orders lower than that of 1R cell. This improvement mainly comes from the connected reverse-biased diode which limits the current flowing through it. The phenomenon is similar to other 1D1R structure reported in [9, 10].
The current level at LRS demonstrates significant rectifying characteristics for both polarities. At ±0.1 V, the F/R ratio can be up to 103, which resulted from the series connection of the diode and capable of suppressing the sneak current effect.
The operation current becomes lower while R HRS/R LRS ratio degrades to approximately 2,300 at +0.1 V. Nevertheless, the ratio is still large enough to distinguish logic ‘1’ and ‘0’. The lower current level can be explained by the fact that for a given applied voltage, there is voltage drop on the diode, and therefore the effective voltage drop on the RRAM is smaller than that of 1R cell. In addition, for positive bias which corresponds to diode operated under forward region because the effective voltage drop on the RRAM directly depends on its resistance state and the nonlinear I-V characteristics of the diode, the R HRS/R LRS ratio becomes degraded.
SET/RESET voltage slightly increases. This is attributed to voltage drop across the diode and therefore a larger voltage is required to form equivalent voltage on the RRAM. Nevertheless, the SET/RESET voltage is still close to 1 V which is beneficial for low-power operation.
Conduction mechanism and retention characteristics
Comparison of main device characteristics for RRAM devices with rectifying property
Set voltage (V)
Reset voltage (V)
F/R ratio (V)
Pt/TiO x /Pt 
Pt/TiO x /Pt
~102 @ 1 V
<102 @ ±0.5
Pt/p-NiO x /n-TiO x /Pt
105 @ ±3
~102 @ 1 V
102 @ ±1
10 @ 1 V
10 @ 4
NiSi/HfO x /TiN 
>103 @ ±1
This work TaN/ZrTiO x /Ni
~2,300 @ 0.1 V
~103 @ ±0.2
This work was supported by the National Science Council of Taiwan under Contracts NSC 101-2628-E-007-012-MY3 and NSC 101-2120-M-009-004.
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