p-Si photodiode with ultra-thin metal cathode

Accepted Manuscript Perovskite/p-Si Photodiode with Ultra-Thin Metal Cathode

Osman S. Cifci, Adem Kocyigit, Pencheng Sun PII:

S0749-6036(18)31112-1

DOI:

10.1016/j.spmi.2018.06.009

Reference:

YSPMI 5744

To appear in:

Superlattices and Microstructures

Received Date:

28 May 2018

Accepted Date:

04 June 2018

Please cite this article as: Osman S. Cifci, Adem Kocyigit, Pencheng Sun, Perovskite/p-Si Photodiode with Ultra-Thin Metal Cathode, Superlattices and Microstructures (2018), doi: 10.1016/j. spmi.2018.06.009

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ACCEPTED MANUSCRIPT

Perovskite/p-Si Photodiode with Ultra-Thin Metal Cathode Osman S. Cifci1, Adem Kocyigit*2 and Pencheng Sun1 1University

2*

of Illinois at Urbana-Champaign, Material Science and Engineering, 61801 Urbana, USA Igdir University, Engineering Faculty, Department of Electrical Electronic Engineering, 76000 Igdir, Turkey

Abstract: Perovskites have attracted great interest because they provide promising improvement for solar cells. Yet, the perovskites have not been extensively used by the researchers for diode applications. In this study, both Al/p-type Si and Al/perovskite/p-type Si devices have been obtained. We used a facile and cost-effective way of making perovskite thin film layer between the ultra-thin metal and semiconductor as an interfacial layer by spin coating technique as well distributed film. In order to keep costs low, aluminum was chosen as the cathode material. The Al/p-type Si and Al/perovskite/p-type Si devices have exhibited good rectifying properties and calculated rectifying ratio of the devices are 2.39 x 103 and 4.56 x 104 at 1 V, respectively. Photodiode properties of the device have been illustrated and discussed in the details by calculating some diode parameters. While the Al/p-type Si device has 1.53 ideality factor value and 0.72 eV barrier height, the ideality factor and barrier height values of Al/perovskite/p-type Si device have been obtained as 2.12 and 0.87 eV, respectively under dark condition. The efficiency and fill factor values of the Al/perovskite/p-type Si device are 7.44 x 10-3 and 23.7, respectively. Such devices can find applications as rectifiers and photodiodes in industry. Keywords: Ultra-thin metal, I-V characteristics, Schottky device, photodiode, perovskite 1. Introduction Perovskites have attracted great interest because they provide promising improvement for optoelectronic devices such as photodetectors, photodiodes, and lasers [1–3]. They have good electrical and optical properties such as high mobility, low excitonic binding energy, long charge carrier time, long diffusion length, low processing temperature, fast charge generation and durable band gap [4]. Specifically, methylammonium halide perovskites (CH3NH3PbX3 X=Cl, I or Br) have exciton binding energy of 20 to 50 mV and high dielectric constant. The bandgap of methylammonium lead iodide, the main phase used in the study, is reported to be between 1.5 and 1.6 eV [5–7]. These properties lead to strong photovoltaic effect or high power conversion efficiency and so, they can be performed as photodiodes or photodetectors [8]. Preparation of perovskite thin films is an area of active research. It is affected by the composition of precursor solution which influences the crystallization and surface morphology of the films [9]. There are many techniques to prepare perovskite thin films such as one-step solution coating [10], vapor phase deposition [11] *

Corresponding author e-mail: [email protected]

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and, sequential deposition [12]. Among them, one-step solution coating technique is straightforward and costeffective [13]. However, preparation of uniform, and pinhole-free perovskite films on planar substrate by using solution deposition is challenging [14]. For example, in the case of CH3NH3PbI3 films island formation leads to reduced surface coverage which reduces the efficiency of the devices [15] and it is very desirable to produce uniform perovskite films in a cost-effective way. Perovskites can also be employed as inter-layer for diode applications but they have not been extensively used by the researchers. There are some studies about investigation of Schottky effect for perovskites. Chen et al. [16] studied Al/CH3NH3PbI3/ITO Schottky diode characterized with XRD, AFM, UV-Vis spectrometer and I-V characteristics. They addressed that surface of the perovskite film was smooth and, it had diode-like characteristics. Pandey et al. [17] reported high-speed perovskite Schottky photodiode on ITO substrate. The perovskite Schottky device had rectifying property and responsivity to the light illumination. Shaikh et al. [8] obtained Schottky-junctions which was formed on CH3NH3PbBr3 single crystals perovskite with an ultra-thin, semitransparent Pt contract. They showed that these devices had good response to the light illumination. However, in a closer look the cathodes used in these studies are either transparent conductive oxides, especially indium tin oxide, or precious metals. Although it finds applications in solar cells, flat-panel displays, and organic light emitting diodes [18], ITO includes indium which is a rare-earth metal. Thus, cost and sustainability of the production is a concern. Ultra-thin metal layers are proposed to overcome this issue [19] and have been employed for several electronics and photonics applications. Those applications include surface plasmon polariton propagation [20], electrodes [21], active modulators [22], and solar thermal applications [23]. However, noble metals are usually used in this study which raises concerns on the cost of production. When the literature is investigated, it becomes evident that cost-effective cathode materials in perovskite devices are highly appealing. Motivated by the lack of Schottky diode structures using perovskites in a cost-effective way, we prepared CH3NH3PbI3-xClx thin film on Si substrate using one-step spin-coating method with ultra-thin Al cathode. The device was investigated in terms of morphological, electrical, and optical properties. 2. Experimental Details To obtain photodiode devices, Si wafer (p-type) was employed as semiconductor and substrate, and it has (100) direction and 7.3 x 1015 cm-3 carrier concentration. The wafer was cut into 1.5 cm x 1.0 cm pieces and then the pieces were cleaned with acetone, water and propanol. For removing native oxide layer and impurities on the surface of the Si wafer, the pieces were submerged into HF:H2O (1:1) solution for just 30 seconds. Aluminum was sputtered back surface of the pieces as Ohmic contact, and they were annealed in N2 atmosphere for 5 minutes at 500 °C. Following the fabrication of back contact, one-step solution growth method was used to grow CH3NH3PbI3-xClx films on the front surface. We followed a similar recipe reported by Zhao and Zhu [13]. Specifically, 520 mg of complex which has equal parts of lead iodide, methyl ammonium iodide, and DMF was mixed with 100 mg methyl ammonium chloride. 1320 mg of DMF solvent was introduced to the mixture. The mixture was spin-coated on Si wafer at 4000 rpm for 25 seconds. Afterwards, the perovskite thin film was annealed in Argon filled glovebox at 100°C for 45 minutes. Once the perovskite film (CH3NH3PbI3-xClx) was ready, 10 nm Al was sputtered using a circular hole array mask to make rectifying 2

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contact. One of piece was used as the Al/p-type Si device without perovskite layer to determine the perovskite layer effect. While the Al/perovskite/p-type Si device was characterized using Raman spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), the I-V measurements was performed to the both Al/p-type Si and Al/perovskite/p-type Si devices under dark and light illumination. In the Raman spectroscopy, the excitation wavelength used in the characterization was 532 nm. Exposure time is fixed at 10 seconds and three measurements were averaged. The objective used had a magnification of 20x with a numerical aperture of 0.45. AFM images were obtained by Asylum Research MFP-3D AFM. Hitachi 4800 model SEM were performed to take surface images of the device. The thickness of the Al rectifying contacts were determined using Dektak 3030 profilometer. While the Keithley 2400 Picoammeter/Voltage Source was employed I-V measurements, Newport Solar Simulator which has 10 mw/cm2 light intensity was used to light exposure to the devices. (a)

(b)

Figure 1. a) Schematic and b) band diagram of Al/perovskite/p-Si device 3. Results and Discussion A schematic and band diagram of the Al/perovskite/p-type Si device is shown in Fig. 1a and 1b, respectively. According to Fig. 1a, an ultrathin Al layer was placed on top of perovskite layer to allow penetration of the light through the Al layer, knocking off more electrons from the perovskite layer. Schematic band diagram of the device in Fig. 1b illustrates how electrons and holes are transported. Fig. 2 shows Raman spectrum of the perovskite thin film. We identified three main peaks in the Raman spectrum. Our perovskite film has both chloride and iodide as halogen. The first peak is at 87.8 cm-1 which 3

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corresponds to asymmetric stretching bond (X-Pb-X where X=Cl or I). This stretching bond was reported at 81 cm-1 for iodine and lead, and at 135 cm-1 for chloride and lead. The second peak is at 307 cm-1 which points out to torsional vibration of methyl ammonium and, this peak has reported to be at 249 cm-1 for iodide, and at 488 cm-1 for chloride [24]. The final peak is observed between 945 and 980 cm-1 which results from C-N stretch. This stretching frequency has reported to be at 960 cm-1 for iodide and 977 cm-1 for chloride [25]. The results match very well with the literature [26] suggesting the presence of desired film.

Figure 2. Raman spectrum of perovskite thin film The surface morphology of the perovskite film surface was studied using AFM. The 2D and 3D AFM images of the perovskite surface are shown in Fig. 3a and 3b, respectively. The perovskite surface on Si wafer is quite smooth and the obtained RMS surface roughness value was about 2.1 nm. Even in a large scan area (625 µm2), the surface roughness was under 5.6 nm. AFM also showed the complete surface coverage of the perovskite film on the silicon substrate. We did not observe any island formation which is detrimental to efficiency of devices [13].

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Figure 3. AFM images of perovskite surface in (a) 2D and (b) 3D for 3 µm x 3 µm scanning areas Surface image obtained by SEM of Al/perovskite/p-Si device have been indicated in Fig. 4. While Fig. 4a and 4b show SEM image of Al rectifier contact, Fig. 4c and 4d display SEM image of perovskite surface. According to Fig. 4a and 4b, the surface of the Al rectifier contact smooth and homogenously sputtered as thin layer (10 nm). We also confirmed its thickness value as 10.93 nm via profilemeter. Fig. 4c and 4d indicates that the perovskite surface has some aggregates. However, the overall surface is smooth because average size of the aggregates is determined to be 16.33 nm according to Image-J software. The small aggregates are more desired for solar cell applications. We achieved to obtain well distributed perovskite film.

Figure 4. Surface morphology images obtained by SEM of Al/perovskite/p-Si device. While (a) and b) shows SEM image of Al contact, (c) and (d) indicates the perovskite surface We have used an ultra-thin metal layer to allow for incoming light to generate extra carriers under the top contact in addition to the generated carriers on the bare perovskite layer. The thickness of top contact was approximately 10 nm which is expected to have a transmission value of about 20% in the visible range [27]. The prepared Al/p-Si and Al/perovskite/p-Si devices were characterized using I-V measurements under dark and illumination conditions. The I-V characteristics of the devices have been displayed in Fig. 5 under dark and light exposure. The devices have exhibited good rectifying (rectifying ratio of Al/p-Si and Al/perovskite/p-Si are 2.39 x 103 and 4.56 x 104 at 1 V, respectively) and photodiode properties according to Fig. 5, but the perovskite layer between Al and p-Si clearly caused to increase the rectifying and photodiode properties. The results can be compared with literature for Al/p-Si devices [28–32]. When a metal-semiconductor device is 5

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exposure to the light, it causes additional charge carriers in the device. In this case, existence of the perovskite thin film with an ultra-thin Al contact (approximately 10 nm according to sputter thickness controller) at the interface has provided more charge carriers at zero bias. As expected, the increase in carriers has caused an increase in the current values of the device at 0 V. This indicates that the device can be used as photodiode or photodetector [33–35]. To better understand the device properties, several diode parameters such as ideality factor (n), barrier height (𝜙𝑏) or series resistance (Rs) should be calculated. Using thermionic emission theory, the barrier height and ideality factor can be obtained from I-V measurements. The current, I, is expressed as follows according to thermionic emission theory: 𝐼 = 𝐼0exp

( )[

(

𝑞𝑉 𝑞𝑉 1 ‒ exp ‒ 𝑛𝑘𝑇 𝑛𝑘𝑇

)]

(1)

where 𝐼0 is saturation current, and it is determined by y-intercept linear region value of the I-V graph. 𝐼0 is given as the below equation: ∗

2

q𝜙𝑏

( )

𝐼0 = 𝐴𝐴 𝑇 exp ‒

k𝑇

(2)

where q, and V, represents an electron charge and applied bias voltage, respectively. k is Boltzmann’s constant and T is the temperature. A and A* shows diode area (7.85 x 10-3 cm2) and Richardson constant (A*= 32 A cm-2 K-2 for p-type Si), respectively. As shown in Table 1, the device has 4.91 x 10-11 A for dark and 1.48 x 10-7 A light illumination saturation current values. The ideality factor (n) and barrier height (𝜙𝑏) are given as below: 𝑛=

( )

q d𝑉 k𝑇 dln𝐼

(3)

and ∗

2

( )

k𝑇 𝐴 𝐴𝑇 𝜙𝑏 = ln q 𝐼0

(4)

n and 𝜙𝑏values were determined via Eqs. (3) and (4) for dark and light conditions and tabulated in Table 1. While ideality factor values were calculated as 1.53 and 2.12 for Al/p-Si and Al/perovskite/p-Si devices under dark, the light illumination caused to increase at the ideality factor values as 3.45 and 5.75 with illumination, respectively. The ideality of the device decreased via perovskite layer and confirmed the perovskite interfacial layer successfully was inserted between the Al and p-Si. According to Table 1, the Al/p-Si device (0.72 eV) has lower barrier height value than the Al/perovskite/p-Si device (0.87 eV), and the light illumination caused to decrease at barrier height values, but the barrier height value of the Al/perovskite/p-Si device decreased more 6

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than the Al/p-Si device. This result can be attributed to that interfacial perovskite layer is sensitive to the light illumination. In addition, the calculated ideality factor value for CH3NH3PbI3-xClx is smaller than obtained from literature [16]. In an ideal diode, the ideality factor value is equal to unity but non-ideal metal-semiconductor devices have bigger ideality factors than one. The bigger n values of the devices are generally attributed to, barrier inhomogeneity [36], tunneling processes [37], image-force effects [38], series resistance [39], nonuniform distribution of the carriers in the interfaces [40] or interface states [41]. The high ideality factor values in these devices can be ascribed to interface states and barrier inhomogeneity [42]. When light exposes to the devices, they strays from ideality because of increasing carrier concentration [8]. The same case is observed here when the devices were exposed to the illumination. Even if devices have light exposure, they have protected their good rectifying properties. Furthermore, applied illumination has caused an increase in the current amount of the Al/perovskite/p-Si device and, for that reason, the device can be used as a photodiode or a photodetector [3].

Figure 5. I-V characteristic of a) Al/p-Si and b) Al/perovskite/p-Si devices for dark and light illumination conditions To calculate the series resistance, another diode parameter, other approximations such as Cheung or Norde technique can be performed on I-V characteristic of the device [43,44]. These techniques can also be used to obtain ideality factor and barrier height. According to Cheung approximation, the current can be expressed as following equation [45,46]:

(

𝐼 = 𝐼0exp ‒

q(𝑉 ‒ 𝐼𝑅𝑠 𝑛k𝑇

)

(5)

where IRs shows the voltage drop owing to the series resistance in the current. The equation (5) is rearranged according to Rs, Eqs. (6) and (7) are obtained as Cheung’s functions. d𝑉 k𝑇 = 𝐼𝑅𝑠 + 𝑛 dln𝐼 q

(6) 7

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( )(

𝐻(𝐼) = 𝑉 ‒ 𝑛

)

k𝑇 𝐼 ln ∗ 2 q 𝐴𝐴 𝑇

(7)

where H(I) can be written as: 𝐻(𝐼) = 𝐼𝑅𝑠 + 𝑛𝜙𝑏

(8)

According to Cheung’s functions, equation (6) and (8) exhibit straight lines while they plotted versus currents. So, the slope and y-axis intercept of the dV/dlnI versus I plot determine Rs and nkT/q which is helps to find n value. In addition, Rs and n𝜙𝑏values are obtained from the slope and the y-axis intercept of H(I) versus I plot. Thus, 𝜙𝑏 is determined one time, but Rs is obtained two times. The two Rs values are used to check the harmony of Cheung’s functions [47]. Table 1. Some diode parameters of the Al/p-Si and Al/perovskite/p-Si devices obtained various method for dark and light illumination conditions Condition

Saturation n (I-V) n Cheung 𝝓𝒃 (I-V) 𝝓𝒃Cheung 𝝓𝒃Norde Current (I0) (eV) (eV) (eV)

Rs Cheung (k (H(I)))

Rs Cheung ((k (dlnI)

Rs Norde (k)

Al/p-Si perovskite

Dark

2.05 x 10-8

1.53

1.67

0.72

0.71

0.74

4.36

4.47

7.60

Light

1.61 x 10-7

3.47

3.46

0.66

0.63

0.66

9.60

9.95

4.22

Dark

4.91 x 10-11

2.12

2.13

0.87

0.85

0.90

338

311

342

Light

1.48 x 10-7

5.75

5.74

0.67

0.65

0.67

4.72

4.19

3.08

Fig. 6a-6d display the dV/dlnI vs. I and H(I) vs. I plots of the Al/p-Si and the Al/perovskite/p-Si devices for dark and light illumination conditions. The n and Rs values of the device were determined for dark and light illumination conditions and tabulated in Table 1. While the series resistance value of the Al/p-Si device increase slightly with illumination, there is a drastically decrease at Rs value from 338 to 4.72 k for the Al/perovskite/p-Si device. This decrease at series resistance has indicated that illumination increased the carrier concentration at the interface of the device [34]. In addition, Rs values obtained from Cheung method are good harmony with each other according to Table 1 for dark and light illumination conditions. This results are confirmed the consistency of the Cheung method. However, there are minor differences between Ideality factor and barrier height values are depended on the approximation differences [48].

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Figure 6. dV/dlnI-I and H(I)-I graphs of Al/p-Si and Al/perovskite/p-Si devices. While (a) and (b) show dV/dlnI-I and H(I)-I plots of the Al/p-Si for dark and light illumination, (c) and (d) display dV/dlnI-I and H(I)-I graphs for Al/perovskite/p-Si devices under dark and light illumination, respectively. Norde’s method can be performed as another technique to calculate the barrier height and series resistances. Mathematical expression of the Norde function are typed as follow [49]: 𝐹(𝑉) =

(

)

𝑉 k𝑇 𝐼(𝑉) ‒ 𝑙𝑛 ∗ 2 𝛾 q 𝐴𝐴 𝑇

(9)

here as ideality factor value, n, is employed calculated thermionic emission theory value. 𝛾 represents an integer value which is bigger and closest to the n. If equation (9) is rearranged, the formulas of the barrier height and series resistance are obtained as next equations: 𝑉0 k𝑇 𝜙𝑏 = 𝐹(𝑉0) + ‒ (10) 𝛾 q

[

]

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𝑅𝑠 =

𝛾 ‒ 𝑛 k𝑇 𝐼 q

(11)

where F(V0) and V0 is the minimum F(V) and voltage values, respectively. F(V)-V plots of the Al/p-Si and Al/perovskite/p-Si devices for dark and light illumination conditions are shown in Fig. 7a and 7b, respectively. The calculated 𝜙𝑏 and Rs values of the devices are listed in Table 1 for dark and light illumination according to Norde functions. While the 𝜙𝑏 values are good agreement which is obtained thermionic emission theory and Cheung’s method, there is some difference for Rs values which is obtained Norde’s and Cheung’s methods. This difference can be attributed to approximation differences between Norde’s and Cheung’s methods [48].

Figure 7. F(V)-V plots of Al/p-Si (a) and Al/perovskite/p-Si (b) device for dark and light illumination Schottky devices can thought as solar cell but their efficiency is lower than traditional ones [49,50]. Photovoltaic properties of metal-semiconductor devices are explained that when the light hit the device, electron-hole pairs produce in the interface of the device and these carriers can be jumped the barrier between the metal and semiconductor easily and caused to increase in the current [45]. We examined the Al/perovskite/p-Si device as solar cell and measured I-V characteristics under solar simulator. In addition, the current increase of the device after the light illumination can be seen in Fig. 4 at reverse biases. Current density (J) versus voltage graph of this device can help to determine the solar cell parameters J-V graph of the Al/perovskite/p-Si device have been indicated in Fig. 8 for power extraction region, and open circuit voltage (Voc) and short circuit current density of the device (Jsc) were determined as 6 mV and 5.23 x 10-2 mA/cm2, respectively. Solar cell efficiency (η) and fill factor (FF) were calculated from below equations [49]: 𝜂𝑝 =

𝐹𝐹 =

𝐽𝑚𝑉𝑚 𝑃0 𝐽𝑚𝑉𝑚 𝐽𝑠𝑐𝑉𝑜𝑐

(12)

(12)

10

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where, JmVm represents maximum power point of J-V, and 𝑃0 is incident light density (10 mW/cm2 for this case). The values of η and FF were 7.44 x 10-3 and 23.7, respectively. The device has lower power conversion efficiency compared to the literature [6,10,51]. Efficiency of the device might be improved using different contact metals or other designs [50].

Figure 8. J–V characteristic of Al/perovskite/p-Si device under illumination 4. Conclusion The Al/p-Si and Al/perovskite/p-Si devices were obtained via ultra-thin Al rectifying contact and characterized. CH3NH3PbI3-xClx perovskite thin film was used as an interfacial layer in the Schottky device to study its morphological and electrical behaviors. The perovskite film for interfacial layer was obtained using cost-effective and straightforward one-step spin-coating technique and, its morphological properties were study by SEM and AFM. According to SEM images, Al contact was sputtered successfully, and perovskite film has smooth and homogenous surface. The AFM images confirmed smooth film surface, and the RMS surface roughness value of the perovskite film 2.1 nm for 3 µm x 3 µm surface areas. The obtained perovskite based device has very good photodiode and rectifying properties (4.56 x 104 at 1V rectifying ratio) according to I-V measurements. Some diode parameters such as ideality factor, barrier height, and series resistance of the devices were calculated using thermionic emission theory, Norde’s and Cheung’s methods. Solar cell parameters were also determined from I-V measurements under illumination. The device is not high solar cell efficiency according to results. Based on these results, performance of the Schottky device can be effectively improved utilizing perovskite interfacial layer, which may potentially lead to efficient optoelectronic devices. References

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ACCEPTED MANUSCRIPT Highlights of Perovskite/p-Si Photodiode with Ultra-Thin Metal Cathode

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We prepared CH3NH3PbI3-xClx thin film on Si substrate using one-step spin-coating method with ultra-thin Al cathode The obtained perovskite thin film exhibited very good distribution. We obtained good rectifying properties from Perovskite/p-Si device using very thin Al layer contact The device has shown good phototdiode properties at reverse biases.