**Disclaimer: There is a ton of extra information here, mostly on the functionality of the diode and if you know most of it you can skip to the end. In all honesty I needed to go over most of it to remember how diodes worked and so I thought I'd type it out**
It has been a little while but it seems like what you are asking is what happens when you increase the forward bias or make it more forward bias. When the device has no bias there is a Vbi barrier that limits the P-side hole and N-Side electron majority carriers this is seen in the website you gave us in figure 4.2.3. Thus the main form of current is due to recombination and generation (which gives the slight negative current). As you increase the voltage, the barrier for those majority carriers decreases from Vbi to Vbi - Va, this gives rise to the diffusion current (which is the current that is due to the excessive holes on the P-side and electrons on the N-side flowing across the junction). A linear change in the Phi yields an
exponential change in the diffusion current (as can be seen in berkeman's equation above). When Vbi = Va there is no electrostatic barrier and the P-side holes and N-side electrons can move freely across the junction and will move due to the diffusion principle.
This then brings us values of Va which are greater than Vbi. Ideally (according to simplifications made to form most of the equations) the current increases exponentially to infinity as the
voltage increases linearly, this is because as you increase the voltage the fermi levels increase and cause there to be more and more majority carriers and therefore more and more current. Picture it like this, in figure 4.2.3 of the site you gave us the device is in equalibrium. if you fix the p-side and move the n-side up, you will eventually get two parallel bands (valence and conductance) with two different fermi levels. As you move the n-side up the majority carriers can still freely cross the junction (actually more easily) because it will "want" to move to a lower potential due to electrostatic principles. The p-side holes will "want" to go to the n-side because the n-side has many more lower energy positions. Same with the electrons vice-versa.
** Start here if you don't need/want to know about the diode functionality**
In the real world problems arise in three ways.
1. At lower forward biases (kT/q < Va < .4v) the R-G current (recombination and generation) still plays a role causing a different equation than the ideal diode equation. Specifically I = Is(exp(qVa/2kT)-1).
2. As you increase the voltage across the junction passed the ideal region (Va > 1v, IIRC) a phenomenon called high-level injuection takes place. Basically, like 1 above some of the assumptions and simplifications taken earlier cause the ideal diode equation to be invalid. And coincidentally the relationship between current and voltage is roughly the same as in 1.
3. As you increase the current running through the semiconductors, the series resistance of the metals begins to play a larger role. I think something like Rs = 1 ohm. So the actual voltage across the junction is Vj = Va - IRs (this is true always but only really matters when the current gets high enough to effect Va). This causes the current to start to plateau as you increase the voltage.
In conclusion.
Yes, Phi does become negative.
The assumed drop of .7 is a rough estimate of the diode in its working condition in the forward bias. A slightly lower voltage will yeild a significantly low current and will therefore not be on, and a slightly higher voltage will yeild (or need to draw) a significantly higher current. Also if you have the current capacity to run at these higher voltages it will run into the problems above.
Again, It's been a little while so I welcome any questions, comments, or criticisms.
D Dean